Roberto González Gómez

Aknowledgments

Pr Jean-François Halet

Dr Jean-Yves Piquemal

Carine Michel

Dr Karine Philippot

Pr Romuald

Laize Zaramello

Jordi Elena Martín Morales

Creus Casanovas

Samuel Drouet

Carlos Álvares Lamsfus

Chen Zhang

Alvaro Fernández Álvarez

Carlos Pinheiro

Luca Digianantonio

Luis Miguel

Martínez Prieto

Israel Cano

Julian Crespo Gutiérrez

Andreas Sergides

Mai-Phuong Yan

Laura

Thiquyen, Elisa, Jorge, Ionut, Mahmoud Lea

Lluìs

Paul, Iskander Adrien B Laurent

Hamlet, Hiroshi Mexico Itzel

Carboxylic Acid-Capped RuNPs: Use of Ligands with Longer Alkyl Chain Length

Development of ruthenium nanoparticles as catalyst models for the splitting of water : combination of experimental and theoretical chemistry approaches

LIST OF TABLES

INTRODUCTION

The search for renewable energy is one the greatest challenges of our modern society.

Even when sunlight can be considered as an almost inexhaustible source of energy, that could bring our world to adopt a new paradigm of sustainable development, harnessing it requires its conversion to storable fuels, such as hydrogen (H 2 ). ([1], [START_REF] Lewis | Light work with water[END_REF]) Having this in mind, this PhD manuscript is an upstream study in the general context of the solar hydrogen production via photocatalytic water splitting, as illustrated in the image hereafter.

Roberto González Gómez 22 Two combined catalytic reactions are involved in the photoproduction of hydrogen from water: hydrogen evolution (HE) and water oxidation (WO). However, each reaction of this green route needs to be improved. The rational design of catalysts, ([3], [START_REF] Li | Nanoscale Advances in Catalysis and Energy Applications[END_REF]) as well as the understanding of their photophysical and catalytic properties, are real challenges. Metal nanoparticles (MNPs) have been reported as efficient HE and WO catalysts. ([5]- [START_REF] Grigoriev | Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers[END_REF]) Such nanomaterials have shown to exhibit high electrocatalytic activities, with respect to WO and HE reactions, with a low overpotential.

Among other factors, comparison with bulk materials brings out the importance of using materials that possess a high surface area as catalysts for water splitting process. The main drawback of such catalysts lies in their cost, which is significantly higher than state-of-the-art catalysts. Therefore, it is necessary to develop MNPs that can be used as a better alternative.

Different ruthenium-based nanomaterials with various composition, morphologies, structures and sizes have been reported in the literature as catalyst for water splitting process. In particular, ruthenium nanomaterials have proven to be interesting alternatives to Pt and Pd based catalysts for HER. [START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] Improvement of the electrocatalytic performance of ruthenium nanoparticles (RuNPs) compared to that of Ru black powder has been established and attributed to the greater specific area that the RuNPs display. Very recently, the potential of RuNPs stabilized with phenylpyridine or MeOH/THF for the HER has been demonstrated. [START_REF] Creus | Ligand-capped Ru nanoparticles as efficient electrocatalyst for the hydrogen evolution reaction[END_REF], [START_REF] Drouet | A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions[END_REF] Regarding RuNPs, despite their diversity, there is still a need to modify their surface in order to improve their properties and functionality. The physical and chemical properties of RuNPs depend on their structural characteristics like their shape, size, defects, but also on the nature of capping ligands used to stabilize them and on the number of adsorbed species onto the metal surface. Although carboxylic acids are widely used as surfactants in colloidal synthesis, the direct adsorption of carboxylic acids onto ruthenium metal surfaces has received less attention.

This PhD thesis provides a reference study in the aim to design a novel class of nanocatalyst for the HER activated by light. To access nanomaterials that can be activated by light, it is required to elaborate hybrid materials that combine MNPs with a photosensitizing molecules grafted on their surface. This can be done for instance through the use of a polypyridyl ruthenium complex that bears pending carboxylic acids groups that can act as anchoring functions.

Roberto González Gómez 23 For this purpose, we started studying the surface properties of RuNPs stabilized by carboxylic acids as model systems. Alkyl chains with different lengths are considered. On the experimental side, RuNPs were synthesized following the organometallic approach using ethanoic (EtAc), pentanoic (PentAc) and octanoic acid (OcAc) as stabilizers. TEM characterization revealed small NPs with a homogeneous morphology and good dispersion. The surface state of these RuNPs was probed by analytical techniques such as IR, WAXS, NMR, etc., leading to a trustful mapping of their surface. Once the optimal ligand ratio to get RuNPs of similar sizes and their synthetic conditions were established, it was possible to determine the influence of the alkyl chain length of the carboxylic acid ligands on the surface properties of the NPs.

In parallel, density functional theory (DFT) calculations were performed according to a thermodynamic model fed with DFT energies. Also, a systematic analysis of the bond properties and of the electronic states (Density of States, Crystal Orbital Hamilton Population, atomic charges) was carried out.

DFT calculations of the vibrational features of model Ru 55 NPs and of the chemical shifts of model [Ru 6 ] clusters also allowed to corroborate the spectroscopic experimental assignations.

Spectroscopic data as well as DFT mechanistic studies showed that the carboxylic acids lie on the metal surface as carboxylates, together with hydrogen atoms. The experimental and theoretical titration results are in good agreement, indicating it as a relevant step to build a model to understand the ligand influence on RuNPs properties.

For the optimal surface composition, the hydrogen adsorption Gibbs free energy was found close to the 0 kcal.mol -1 criterion which, according to the seminal work of NØrskov et al., [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] makes these RuNPs a promising HEC. As a result, the best nanocatalyst revealed to have both, intermediate crowded metal surface and intermediate alkyl chain length for the capping ligand, indicating the RuNPs stabilized by pentanoic acid as the most promising catalyst.

Since RuNPs are known to be active catalysts for the reduction of arenes, the direct use of a polypyridyl complex as stabilizer during the synthesis of RuNPs under hydrogen atmosphere may lead to the reduction of the bipyridine ligands. To circumvent this potential issue, synthesis PS-modified RuNPs can be envisaged by a ligand exchange method. For this purpose, exchange ligand viability studies have been performed starting from RuNPs pre-stabilized with octanoic acid and exposed to incoming ligands (benzoic and trifluoroacetic acids). Moreover, theoretical studies on the reliability of this procedure with actual photosensitizers, namely [Ru(bpy) x (bpy-(RCOOH) x ) 3- x ] 2+ , were performed.

This thesis dissertation is divided into six chapters.

The first chapter gives a general overview to situate this work in the current context based on bibliographic data. In general, it presents the interests of metal nanoparticles (MNPs) according with their novel properties. Furthermore, a focus is given on the synthesis and catalytic properties of RuNPs. Also, DFT methods for modelling MNPs are described.

The second chapter is dedicated to the experimental and theoretical description of RuNPs stabilized by ethanoic acid, where it can be found a complete surface mapping of this optimized nanosystem together whit its viability for HER.

Meanwhile, in chapter three the optimal surface coverage of RuNPs stabilized by pentanoic and octanoic acid is described by a combination of experimental and theoretical tools.

The viability of these catalysts and the ligand alkyl chain length influence on the formation and activity of RuNPs are deeply discussed.

In the fourth chapter are presented studies of ligand exchange at the surface of preformed RuNPs stabilized by octanoic acid when adding benzoic or trifluoracetic acids. These studies were boarded as prove of content for the viability of this strategy to anchor photosensitizers with carboxylic acid pending groups onto the surface of preformed RuNPs. This approach has been theoretically studied as presented in the chapter five.

The sixth chapter deals with the experimental and theoretical techniques used for the development of this PhD work. At the end of the manuscript, several appendices can be found that include the calculated DFT energies and general information utilized for theoretical calculations.

As a general view, this research work was designed in order to bring a better understanding of the structure/properties relationship at the nanoscale, aiming to explain the surface properties of RuNPs directly stabilized by carboxylic acids and their catalytic viability. The major contribution of this thesis is to closely combine experimental and theoretical studies to access a deep knowledge in the surface properties of the described RuNPs systems.

CHAPTER I

Roberto González Gómez 25

CHAPTER I

Roberto González Gómez 27

Metal Nanoparticles: Interests, Properties and Applications

In the past twenty five years, metal nanoparticles (MNPs) have been strongly attracting the attention of the scientific community and enterprises due to their unique properties located between those of bulk materials and molecules. ([11], [12]) It is well-known that controlling the structure of these nanomaterials can directly influence their physical and chemical properties, that can be of interest for applications in various fields ranging from biology, medicine, optoelectronics, catalysis, energy, etc. [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] Especially, their catalytic reactivity can be tuned by a fine control of their structure, [START_REF] Iii | A review of modern transition-metal nanoclusters: their synthesis, characterization, and applications in catalysis[END_REF] leading to novel characteristics contrasting to that exhibited by molecules and bulk materials. ([15], [START_REF] Kim | Synthesis, Characterization, and Application of Ultrasmall Nanoparticles[END_REF])

MNPs have a different chemical and physical behaviors due to their electronic change when reaching a critical nanoscale size, [1 -100 nm]. For example the decrease in its boiling and melting point [START_REF] Castro | Size-dependent melting temperature of individual nanometer-sized metallic clusters[END_REF] or the change in its optical properties (color). [START_REF] Schmid | Metal Nanocluster in Catalysis ad Materials Science: The Issues of Size Control[END_REF] In comparison to bulk materials, the size reduction towards the nanoscale carries a decrease in the electron mobility (delocalized electrons) that leads to quantum size effects (QSE). [START_REF] Roduner | Size matters: why nanomaterials are different[END_REF] As a consequence, the properties of MNPs do not follow the same rules as those of bulk materials because of the appearance of particular nano-effects.

The particular properties of MNPs can be explained in terms of QSE by describing the relationship between the valence and conduction band in these materials. In bulk metals these bands at some point overlap leading to a partial occupation of the conduction band by the valence electrons (s & d). This lets highly mobile electrons which are responsible for the electrical conductivity of these materials. When the valence and conduction bands are slightly separated by a gap, materials act as semiconductor materials. However, if the observed gap is too large, materials are named as insulators.

The continuum band existing in bulk metals begins to separate when the quantity of metal atoms in the material decreases which is the case in nanomaterials. Meaning that the band overlapping does not longer exist, and the material tends to be a semiconductor. The gap between the valence and the conduction bands increases while the material size decreases till getting a similar situation as for molecular entities where discrete energy levels exist (figure 1.1). At this CHAPTER I

MNPs Properties and Applications

Roberto González Gómez 28 point, the properties of bulk metals are replaced for those of quantum dots which follow the quantum mechanical rules. This induces a change in the electronic properties of nanomaterials, making it metal nanoparticles to display intermediate properties comparatively to those of bulk metals and molecular species. [START_REF] Guczi | Metal Nanocluster in Catalysis ad Materials Science: The Issues of Size Control[END_REF] Figure 1.1 Energy level diagram from bulk metal to molecular moieties.

The previous phenomenon is particularly true for metal nanoparticles in the size range [1 -

10 nm] because they are expected to exhibit an intermediate state among bulk metal and molecular moieties. As it was described, in this size range the properties of the material is highly dependent on the number of metal atoms held into the nanocluster, this phenomenon is explained due to the change in the quantized energy levels, the so-called quantum size effect

(figure 1.2).
Roberto González Gómez 29 Additionally, the properties of MNPs are dependent of the number of metal atoms present at their surface compared to the ones of the core. The surface to volume ratio increases with the size reduction of the MNPs, which makes very small NPs to have high quantities of surface atoms.

Given their higher surface-to volume ratio compared with bulk metal entities (figure 1.3), MNPs display higher numbers of potentially active surface sites, making them to be highly attractive systems for several applications such, as catalysis. [START_REF] Narayanan | Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability[END_REF] Figure 1.3 Comparison of the surface area in bulk materials and metal nanoparticles.

Roberto González Gómez 30

Furthermore, nanoparticles can be tuned with different shapes (like spheres, cubes, wires, etc.) and diverse crystallographic facets. MNPs can be designed to contain different types of atoms depending on their location in corners, faces or edges, that will present different reactivity properties, which can be of interest for selective catalysis. [START_REF] Narayanan | Can the observed changes in the size or shape of a colloidal nanocatalyst reveal the nanocatalysis mechanism type: homogeneous or heterogeneous?[END_REF] Well-crystallized MNPs have close packed structures (bcc, fcc or hcp) where the central atom is surrounded by successive layers of atoms in order to decrease their surface energy. They are considered as full-shell clusters and the magic number rules for them can be applied, allowing to obtain several data on the different atoms presented in the outer and inner shell of the materials. [START_REF] Tsybukh | A comparative study of platinum nanodeposits on HOPG (0001), MnO(100) and MnOx/MnO(100) surfaces by STM and AFM after heat treatment in UHV[END_REF] For example, a full-shell cluster containing a total of 13 atoms, which is the smallest possible size, apart from the central atom, the surface layer is made of 12 atoms corresponding to the maximum possible coordination number. Larger clusters will contain a total number of atoms as 55, 147, 309, etc., leading to NPs of ca. 1.1, 1.6 and 2.0 respectively, in the case of ruthenium.

The ratio of surface metal atoms in NPs is accessible by knowing the NP crystalline structure and the mean size. [START_REF] Schmid | Two, four, five-shell clusters and colloids[END_REF] In addition, it is possible to calculate the approximate number of metal atoms depending on their location at the surface of the NPs, i.e. edges, corners and faces (table 1.1). [START_REF] Rossell | SACs o nuevos catalizadores formados por átomos metálicos aislados sobre un soporte[END_REF] It can be observed that smaller the NPs are, higher their surface atom numbers are. Some NPs have been reported to be complete full-shell clusters, among them gold NPs, such as Au 55 [P(C 6 H 5 ) 13 ] 12 Cl 6 . [START_REF] Schmid | Hexachlorododecakis (Triphenyl-Phosphine) Pentapentacontagold, Au55[P(C6H5)3]12Cl6[END_REF] Roberto González Gómez 31 Thus, at very small sizes ([1.0 -2.0 nm]) the properties of MNPs can be highly variable due to their difference in metal surface area, size, shape, composition, crystalline structure, etc.

Therefore, a precise control of MNPs size, stability and reactivity becomes crucial. Meaning that the synthesis of MNPs has a major impact or a direct correlation in modifying the energy gap, which is part of the novel properties of these materials.

The potential of MNPs in catalysis has been known since decades through the development of heterogeneous catalysts where metal nanoparticles are deposited into a support. [START_REF] Serp | Nanomaterials in Catalysis[END_REF] In the last 25 years, the field of MNPs has known a renewed interest with numerous efforts devoted to their controlled synthesis, which is a great advantage for an accurate study of their catalytic properties and make them suitable for a target reaction.

The use of MNPs in catalysis (figure 1.4) is based on the assumption of their high metal surface area, where surface active sites may have a direct interaction with the substrates, thus CHAPTER I

MNPs Properties and Applications

Roberto González Gómez 32 mimicking homogeneous catalysts. But due to their low solubility in reaction solvents, which depends on the stabilizing agents used for their synthesis, MNPs are often described as a semi-heterogeneous catalyst. [START_REF] Roucoux | Reduced transition metal colloids: a novel family of reusable catalysts?[END_REF] Moreover, catalysis is considered as colloidal when MNPs form stable suspensions in the reaction solvent (aqueous or organic). In the other hand, supported catalysis concerns to MNPs deposited onto or in the pores of a support (carbon-based materials, metal oxide materials such as SiO 2 , TiO 2 , Al 2 O 3 , etc.).

Figure 1.4 Nanocatalyst are claimed to have better activity and selectivity than that of bulk materials. [28] Published studies have demonstrated that metal nanoparticles are more active than their bulk metal material counterparts for several catalytic reactions ([14], [START_REF] Zahmakıran | Metal nanoparticles in liquid phase catalysis; from recent advances to future goals[END_REF], [START_REF] Na | Colloidal metal nanocatalysts: synthesis, characterization, and catalytic applications[END_REF]) Some of these reactions are for instance:

 Reforming reaction  Hydrocracking  Heck type couplings  Hydrogenation  Oxidations  McMurry couplings  Hydrosilylation  Suzuki couplings  Cycloadditions
Since the last five years, there has been an increased interest in the use of MNPs for the catalytic water splitting reaction. It has been shown by several groups that nanomaterials can be more active than their bulk metals in both hydrogen evolution reaction (HER) [START_REF] Tan | Platinum nanoparticle during electrochemical hydrogen evolution: adsorbate distribution, active reaction species, and size effect[END_REF] and oxygen evolution reaction (OER) [START_REF] Risch | Atomic structure of cobalt-oxide nanoparticles active in light-driven catalysis of water oxidation[END_REF] (figure 1.5).

Roberto González Gómez 33

Figure 1.5 MNPs used in the water splitting reaction. a) HER [START_REF] Tan | Platinum nanoparticle during electrochemical hydrogen evolution: adsorbate distribution, active reaction species, and size effect[END_REF] & b) OER. [START_REF] Risch | Atomic structure of cobalt-oxide nanoparticles active in light-driven catalysis of water oxidation[END_REF] Since a precise control of the MNPs characteristics (size, shape, crystalline structure, etc.), stability and surface reactivity are crucial for their application in catalysis, different synthesis tools have been developed.

Synthesis of Metal Nanoparticles

With the noticeable exception of some 11 superatomic clusters that are electron-and atom-precise compounds, ([33]- [START_REF] Fernández | Trends in the structure and bonding of noble metal clusters[END_REF]) nanostructures with well-defined structures (nanoclusters) are not often found in the literature. In most cases, nanosystems presenting a lower crystalline order in their outer and inner structures are reported. This is particularly true for very small NPs which are often less crystallized. In this context the materials are named as nanoparticles, nanostructure, colloids or nanosystems.

There are two main methodologies to synthesize MNPs (figure 1.6). The top-down procedure involves the granulating of bulk materials to reduce their size by different physical methodologies (thermal and mechanical) or chemical grinding and the subsequent stabilization of the generated material by adding a protective agent. Nevertheless, this approach produce irreproducible materials with non-controlled size. [START_REF] Fedlheim | Metal nanoparticles: synthesis, characterization and applications[END_REF] The other technique, bottom-up, is widely used by the scientific community interested in catalysis because it can provide nanoparticles with well-controlled size, structure and surface which is crucial for designing a reliable catalyst. Additionally, this methodology allows to get CHAPTER I

Synthesis of MNPs

Roberto González Gómez 34 reproducible nanosystems that can be deeply analyzed and characterized. This approach is based on the release of metal atoms, followed by their nucleation into seeds or nuclei and then the growth of NPs till certain size is reached. The growth is determined by the reaction medium or/and the presence of protective ligands. [START_REF] Corain | Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size Control[END_REF] Figure 1.6 Main approaches for the synthesis of MNPs.

[38]

Synthesis of MNPs in Solution

Our goal in this work was to synthetize well-defined metal nanoparticles which can be studied by an experimental and theoretical approach. Therefore, a bottom-up type of synthesis was chosen. MNPs can be formed in diverse ways, either in vapor (flame synthesis) [START_REF] Kammler | Flame Synthesis of Nanoparticles[END_REF] or solution.

Due to experimental performance, instruments and basically to the difficulties met in the NPs synthesis, solution methodology was selected as the synthesis approach of MNPs.

Various methods for the synthesis of MNPs in solution have been developed, such as:

 Chemical precipitation or salt reduction [40]  Hydrothermal method [41]  Photochemical or sonochemical decomposition [42]  Electrochemical reduction [43]  Organometallic decomposition [44]  Sol-Gel method [45]  Polyol method [46]  Radiation induced synthesis [START_REF] Roginsky | Eine neue methode der herstellung kolloider lösungen[END_REF] CHAPTER I

Synthesis of MNPs

Roberto González Gómez 35 Synthesis of MNPs in solution usually offers homogeneous populations with narrow size distributions. However, this depends on the mechanism of NPs formation and consequently on the reaction conditions.

Formation Mechanism of MNPs

The uniformity and reproducibility of MNPs populations depend on the nucleation mechanism and the subsequent growth of them. [START_REF] Roucoux | Reduced transition metal colloids: a novel family of reusable catalysts?[END_REF] Whilst the formation of MNPs has been described by the LaMer mechanism for supersaturate reaction media, however this approach was not accurate enough to describe diluted systems. [START_REF] Lamer | Theory, production and mechanism of formation of monodispersed hydrosols[END_REF] The gradual formation of nanoparticles is based on a three step process: nucleation, growth and agglomeration. [START_REF] Turkevich | A study of the nucleation and growth processes in the synthesis of colloidal gold[END_REF] In the past decade, a four-step general mechanism has also been published for the salt reduction method that consist in two autocatalytic surface steps, namely growth and bulk formation stages (scheme 1.1). ([50], [START_REF] Besson | A Mechanism for Transition-Metal Nanoparticle Self-Assembly[END_REF])

Roberto González Gómez 36 When the nucleation step is started with the reduction of the metal salt, the zero-valent atoms approaches to each other to form irreversible metal seeds whose viability depends on the saturation of the solution. Then, the first autocatalytic process (growth) happens through the diffusion of metal nuclei to the preformed seeds. Later, if the previous step does not stop, the formed nanosystems start to get closer and to form aggregates and later on bulk materials.

Therefore, the presence of a stabilizer that prevents the two last steps is required in order to obtain MNPs. Thus, the growth process is a crucial step that underlines the importance of the stabilizing agent in order to control the MNPs size and morphology.

Nevertheless, the production of homogeneous nanoparticles in size and morphology depends greatly on the differentiation between nucleation and growth processes. When these CHAPTER I

Synthesis of MNPs

Roberto González Gómez 37 processes are overlapped, the growth procedure will depend on the specific type of seeds formed during the nucleation procedure, so-called Ostwald ripening. [START_REF] Hansen | Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?[END_REF] If no differentiation is observed, then an heterogeneous nanosystem will be produced. As a counterpart, homogeneous systems population will be observed if the processes can be differentiated (scheme 1.2).

Scheme 1.2 Heterogeneous and homogeneous formation of MNPs according to the growth process.

Stabilization of MNPs

MNPs possess a high quantity of surface energy which makes them thermodynamically unstable. In order to reduce this phenomenon, particles tend to attract each other in the absence of repulsive forces, which leads to their agglomeration and coalescence. [START_REF] Schmid | Metal Nanocluster in Catalysis ad Materials Science: The Issues of Size Control[END_REF] Thus, it is necessary to avoid the continuum growth of MNPs to elude the formation of aggregates or bulk materials by adding a ligand barrier, namely as stabilizing agent, aiming to produce homogeneous and well-defined MNPs (figure 1.7). [START_REF] Jia | Colloidal metal nanoparticles as a component of designed catalyst[END_REF] Roberto González Gómez 38 There are mainly four different modes of stabilization (figure 1.8): electrostatic (ammonium salts), steric (polymers, dendrimers, ligands), electrosteric (polyoxoanions) and solid supports (zeolites, silica). [START_REF] Ott | Transition-metal nanocluster stabilization for catalysis : A critical review of ranking methods and putative stabilizers[END_REF] Figure 1.8 Representation of MNPs stabilized by electrostatic interactions, polymers and organic ligands, respectively. [START_REF] Ott | Transition-metal nanocluster stabilization for catalysis : A critical review of ranking methods and putative stabilizers[END_REF] Steric stabilization mode allows to prepare homogeneous MNPs that are surrounded by a protective layer. Polymers and dendrimers, such as PVP [START_REF] Bonet | Synthesis of monodisperse Au, Pt, Pd, Ru and Ir nanoparticles in ethylene glycol[END_REF] or PAMAM [START_REF] Crooks | Dendrimer-encapsulated metal nanoparticles: synthesis, characterization, and applications to catalysis[END_REF] , are examples of stabilizers, being generally considered to have a low interaction with the metal surface. Ligands can have covalent interactions with MNPs that generally provides well-defined particles. The σ or π donation/back-donation to the metal surface of thiols, amines and phosphines are examples of these ligands which have been widely used. The donor strength of the stabilizing agent influences strongly the size and morphology of the nanosystems. [START_REF] Amiens | Organometallic approach for the synthesis of nanostructures[END_REF] CHAPTER I

Synthesis of MNPs

Roberto González Gómez 39

Polymers or ligands are common stabilizers that can act against MNP continuous growth by forming an efficient barrier and allow obtaining homogeneous populations of well-defined MNPs. They can be used in the organometallic approach which is a well-known procedure to have at disposal well-controlled MNPs.

Synthesis of MNPs by the Organometallic Approach

The organometallic approach is a powerful method to produce homogeneous MNPs in solution. It is based in the use of organometallic complexes which typically have metal-carbon bonds (M-alkyl, M-olefin, etc.) that can be broken, hydrogenated or even displaced in mild reaction conditions (T, p). Ligands displacement or their decomposition generate uncoordinated metal atoms that thus constituting the metal source for the formation of MNPs.

This approach was first applied to form nickel nanopowders by the decomposition of a nickel organometallic complex ([Ni(C 5 H 5 ) 2 ]) under hydrogen. [START_REF] Pleass | Kinetics of the Deposition from Solutions of Nickel Onto Powder Surfaces of Dicyclopentadienylnickel[END_REF] But later on, the hydrogenation of several metal complexes in the absence of any extra ligands was observed to generate bulk metal materials. [START_REF] Tschan | Ruthenium Metal Nanoparticles in Hydrogenation: Influence of Phosphorus-Ligands[END_REF] Therefore, the addition of a stabilizing agent is crucial to get stable MNPs. Various stabilizers have been used, in particular in the case of RuNPs, which allowed to develop this approach and get a large panel of particles. [START_REF] Philippot | Organometallic Ruthenium Nanoparticles and Catalysis[END_REF] The organometallic approach (scheme 1.3) in essence treats with the decomposition in solution of an organometallic complex (or in some cases a metal-organic complex) in the presence of hydrogen (H 2 ) or carbon monoxide (CO) in mild conditions (low temperature and gas pressure).

The minimum amount of stabilizing agent is added in order to limit the quantity of organics at the metal surface, but this depends on the systems. Olefinic complexes are generally preferred because they easily decompose under hydrogen at low temperature. The use of hydrogen allows avoiding the presence of derivatives from strong reductant agents such as NaBH 4 . [START_REF] Solomon | Synthesis and Study of Silver Nanoparticles[END_REF] Moreover, the release of alkanes that result from ligand hydrogenation is not an issue because they are inert towards the metal surface and can be easily eliminated under high-vacuum. This approach allows thus to limit the presence of pollutants at the metal surface. [START_REF] Amiens | Organometallic approach for the synthesis of nanostructures[END_REF] Roberto González Gómez 40

The control of the growth of the NPs is possible by the addition of a stabilizing agent which can be a polymer or a ligand. Various ligands have been explored, in particular for RuNPs, being considered as strong or weak ligands depending on their interaction with the metal surface. [START_REF] Salas | Influence of amines on the size control of in situ synthesized ruthenium nanoparticles in imidazolium ionic liquids[END_REF] Scheme 1.3 Representation of the synthesis of MNPs by the organometallic approach.

The organometallic approach implies to have adequate metal complexes (which mostly are air or water sensitive and require to be handled under inert atmosphere) as metal source. It presents several advantages that allow to produce MNPs having a clean metal surface and a specific amount of added ligands that protect them from agglomeration and coalescence. The ability to use different types of stabilizers (polymers or organic ligands) is exploited in favor to design specific MNPs sizes and morphologies with tailor-made properties. [START_REF] Rempp | Tailor-made networks: synthesis and properties[END_REF] As it will be seen later, this methodology was used in this work in order to synthesize model RuNPs with the aim to have a better control of the structure/properties relationships and after to design appropriate nanocatalysts for the water-splitting process.

The types of organometallic complexes commonly used for this technique are enlisted hereafter.

 Carbonyl complexes: [Fe(CO) 5 ];

[Ru 3 (CO) 12 ]  Olefinic complexes: [Ni(COD) 2 ]; [Ru(COD)(COT)]  Alkyl complexes: [Pt(CH 3 ) 2 (COD)]  Allyl complexes: [Co(η 3 -C 8 H 13 )(η 4 -C 8 H 12 )]; [Rh(η 3 -C 3 H 5 ) 3 ]

DFT for Modeling Organometallic Nanocatalysts

Nowadays, several technological and industrial processes are based on the use of catalytic processes, leading to a more efficient industry. This issue produced better life conditions, however it also generated environmental problems. In order to solve these problems, the scientific CHAPTER I

DFT for Modeling

Roberto González Gómez 41 community has rulled out the importance of disposing more efficient catalysts and possibly which are environmentally friendly composed of earth abundant materials. [START_REF] Thomas | Principle and Practice of Heterogeneous Catalysis[END_REF] This concerns heterogeneous MNPs but also modern nanocatalysts (either in solution or dispersed into a support) which are in general better defined.

Due to the surface interaction of the catalysts with the substrates, their viability and efficiency are determined by their electronic structure which is also intrinsically related to the structure and composition of the catalysts (figure 1.9). [START_REF] Nørskov | Towards the computational design of solid catalysts[END_REF] Therefore, it is possible to design or choose between several types of catalysts for a specific chemical reaction. Theoretical descriptions of solid catalysts are of high importance because they study the adsorption-desorption phenomena of the substrates onto catalysts, which is a crucial step for knowing their reliability and selectivity. [START_REF] Nilsson | Chemical Bonding at Surfaces and Interfaces[END_REF] Figure 1.9 Representation of the link between MNPs structure-composition, electronic structure and catalytic activity (e.g. HER).

Since a couple of decades, Density Functional Theory (DFT), despite some weaknesses (such as a bad description dispersive van der Waals interactions) and the unpleasant profusion of functionals, is considered as a tool of choice in the rationalization of the performance of heterogeneous ([66], [START_REF] Sautet | Catalysis and surface organometallic chemistry: a view from theory and simulations[END_REF]) and homogeneous catalysis.

Regarding heterogeneous catalysis, the standard strategy consists in the description of the catalysts by slab models and in taking advantage of periodic-DFT calculations. Such methodologies are also designed to efficiently describe the electronic density of metallic systems, i.e. they successfully solve the problem of SCF convergence due to the degeneracy of electronic states at CHAPTER I

DFT for Modeling

Roberto González Gómez 42 the Fermi level. This is why in the present work, although it was considered finite-size ruthenium nanoparticles, it was used one of the reference periodic DFT software, VASP. ([68], [START_REF] Kresse | Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[END_REF])

Since the seminal work of Thomas and Fermi ([70], [START_REF] Fermi | Zur Quantelung des idealen einatomigen Gases[END_REF]) and later on of Kohn and Sham, [START_REF] Kohn | Quantum density oscillations in an inhomogeneous electron gas[END_REF] DFT has revolutionized modern computational chemistry, thanks to the Generalized Gradient Approximation (GGA) functionals, such as PBE. [START_REF] Perdew | Generalized Gradient Approximation Made Simple[END_REF] They are fast enough to allow the treatment of extended systems and are more accurate for describing reaction energies or the relative stability of isomers than the Local Density Approximation (LDA). [START_REF] Kohn | Quantum density oscillations in an inhomogeneous electron gas[END_REF] This is the functional used in this work, although in the molecular DFT, GGA functionals are nowadays replaced by the so-called hybrid functionals, which contain a fraction of Hartree-Fock exchange.

Even so, using hybrid functionals in periodic-DFT calculations increases the computational cost by an order of magnitude, and it does not significantly improve the description of metallic systems, although it has been proven that it can slightly change the picture regarding the preferred grafting sites of adsorbates and the associated energies. [START_REF] Stroppa | CO adsorption on metal surfaces: A hybrid functional study with plane-wave basis set[END_REF] However, GGA functionals such as PBE or revised-PBE [START_REF] Hammer | Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals[END_REF] have proven their ability to successfully address catalytic processes on transition metal surfaces and alloys. [START_REF] Hammer | Theoretical Surface Science and Catalysis-Calculations and Concepts[END_REF] 1.

Methods for Describing MNPs

Several methodologies for describing the electronic properties of metal surface have been reported in the literature. Each one of them can be useful for obtain the morphology of MNPs, specify their crystallinity, describe the MNPs core or inner shell or the optimization of geometries due to the relationship between crystalline structure and morphology. These methods are enlisted hereafter.

 Wulff construction theorem [76]  X-ray diffusion for RDF profiles [77]  Monte Carlo method [78]  Reverse Monte Carlo method [START_REF] Mcgreevy | Reverse Monte Carlo modelling[END_REF] CHAPTER I

DFT for Modeling

Roberto González Gómez 43

Strategy Used to Define the Surface of MNPs

One strategy for modeling MNPs is to consider them as an assembly of the crystallographic planes they exhibit in the synthesized nanoparticles. Each surface is modeled by a metal slab and it is possible to take advantage of this periodicity in order to efficiently solve the Schrödinger equation. For example, in order to account for the possible specificity of the surface chemistry of each crystallographic plane, a 2.0 nm hcp RuNPs should be modelled at least by (101 ̅ 0), (101 ̅ 1) and

(0001) planes. On top of that, the steps that have been proven to exist in such NPs must be modeled by high index crystallographic planes, such as the (101 ̅ 5) plane which accounts for the socalled B 5 sites. [START_REF] Honkala | Ammonia synthesis from first-principles calculations[END_REF] This methodology is a well-defined approach for very large NP, but it involves representing the whole nanoparticle by several planes, which makes it a computationally prohibitive method for NPs that have complex shapes. Another hybrid approach, such as the one depicted in figure 1.10 in case of a PtNP deposited on a substrate, [START_REF] Viñes | Methane activation by platinum: Critical role of edge and corner sites of metal nanoparticles[END_REF] consists in describing the exhibited surface of the PtNP by a slab and its corners and lateral walls by an appropriate mid-size NP.

Figure 1.10 Representation of a PtNP supported onto an oxide substrate (support). The PtNP exhibits a combination of a Pt (111) slab layers for the inner facets and Pt 79 nanoparticles for modeling the edge, corner, and nearby sites. [START_REF] Viñes | Methane activation by platinum: Critical role of edge and corner sites of metal nanoparticles[END_REF] Roberto González Gómez 44 Although, synthetized nanoparticles may possess different irregularities in their structure, as well as complex shapes, and it is difficult to describe or model them as a superposition of infinite crystalline structures. Therefore, the inclusion of different reactive sites as B 4 or B 5 or of corrugated surfaces makes theoretical calculations more reliable. [START_REF] Honkala | Ammonia synthesis from first-principles calculations[END_REF] This methodology was not used in this work because the experimental RuNPs are small ([1 -2 nm]) and should be considered as a superposition of edges and corners rather than a superposition of infinite crystallographic planes. Leaving aside the fact that finite size effects make their electronic structure different from the bulk metal.

Therefore, the nanosystems considered in this work are modelled by large clusters. This methodology offers the possibility to observe the whole nanoparticle as a single entity considering different types of surface and reactive sites. This provides a better representation of the experimental features. It has been shown with this approach that it is possible to account for several surface properties (IR, surface composition, etc.) observed in experiments. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] The model developed in the previous reference (see section 6.2.1) is a spherical 1.0 nm hcp crystal, with two (0001) planes, sidewalls reminiscent of (101 ̅ 1) planes, a corrugated surface and a tip that models B 5 and B 4 sites. It is an all-in-one model that represents the diversity of colloidal ([1 -2 nm]) RuNP. In the framework of periodic-DFT methods, it is described inside a unitcell, with a vacuum large enough to avoid spurious interactions between the cluster and its periodic images (figure 1.11).

Roberto González Gómez 45

Ruthenium Nanoparticles

Ruthenium is a d8 transition metal ([Kr] 4d 7 5s 1 ) with an atomic mass of 101.01 g.mol -1 .

This electron rich metal was discovered in 1843 by the Russian G. Klaus. Ruthenium is isolated from other metals by a series of chemical processes which final stage is the hydrogen reduction of ammonium ruthenium chloride. This metal is not easily oxidized, however under oxygen pressure forms its more stable oxide (RuO 2 ). [START_REF] Seddon | The chemistry of ruthenium[END_REF] For many years, ruthenium-based catalysts have been used in the industry for a wide range of chemical reactions or even in technological devices. For example, Ru 3 (CO) 12 has been applied as catalyst to produce ammonia [START_REF] Muhler | Ruthenium as Catalyst for Ammonia Synthesis[END_REF] or acetic acid. [START_REF] Zhang | Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2[END_REF] Other ruthenium derivatives are also used for olefin metathesis, [START_REF] Weskamp | A novel class of ruthenium catalysts for olefin metathesis[END_REF] oxidations or hydrogenations. [START_REF] Naota | Ruthenium-Catalyzed Reactions for Organic Synthesis[END_REF] Due to its chemical and physical properties, ruthenium has been used in several catalytic processes. However, in order to increase its profitability, the scientific community focused on extending its activity and selectivity. Owing to their intermediate properties between those of bulk materials and molecular complexes, ruthenium nanoparticles (RuNPs) have been developed with high interest. It is expected from their high surface to volume ratio to get a high active surface.

CHAPTER I Ruthenium Nanoparticles

Roberto González Gómez 46

Synthesis of RuNPs

RuNPs were first synthetized by the reduction of RuCl 3 in the presence of borohydrides and surfactants. [START_REF] Nakao | Preparation of noble metal sols in the presence of surfactants and their properties[END_REF] Then, the nanoparticles were carried on under softener conditions aiming to design better homogeneous nanoparticles. In this way, RuNPs were also produced by the reduction of RuCl 3 in polyol. [START_REF] Viau | Ruthenium Nanoparticles: Size, Shape, and Self-Assemblies[END_REF] This method, so-called "the polyol method" has the advantage to allow the formation of RuNPs in milder conditions and to provide more homogeneous populations of NPs while using only a polyol as both reducing and stabilizing agent. [START_REF] Fiévet | The polyol process: a unique method for easy access to metal nanoparticles with tailored sizes, shapes and compositions[END_REF] Also, ligands can be added in order to tune the RuNPs characteristics.

Another efficient approach to produce RuNPs is the organometallic approach which is the method chosen in this PhD work. It is based on the decomposition of a ruthenium organometallic complex under mild reaction conditions and in the presence of a stabilizing agent. As a consequence, monodisperse RuNPs can be obtained with a clean surface (absence of side products). [START_REF] Philippot | Organometallic approach to the synthesis and surface reactivity of noble metal nanoparticles[END_REF] Different organometallic precursor have been used to synthetize RuNPs (figure 1.12)

among them it can be found metal carbonyl complexes ([Ru 3 (CO) 12 ]) and allyl/olefin complexes such as [Ru(COD)(η 3 -C 3 H 5 ) 2 ]. [START_REF] Lee | Hydrogenation of Ru (1, 5-cyclooctadiene)(η3-C3H5) 2 over Black Platinum. A Low-Temperature Reactive Deposition of Submonolayer Quantities of Ruthenium Atoms on Platinum with Real Time Control over Surface Stoichiometry[END_REF] However, the most employed complex is the ruthenium(1,5-

Roberto González Gómez 47

The RuNPs synthetized by the organometallic approach generally present an hcp crystalline structure as for bulk ruthenium, and this even for amorphous RuNPs. But following other synthetic methodologies such as chemical reduction, formation of fcc RuNPs has been observed. It is worth to mention that these fcc RuNPs have presented a different catalytic activity than that of hcp RuNPs. [START_REF] Kusada | Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction Method[END_REF] Therefore, the reproducible control of the synthesis conditions is a crucial point for the study of RuNPs and their possible catalytic applications.

Stabilization of RuNPs

The nature of the stabilizing agent (ligand barrier) employed for preparing RuNPs can be adapted in order to obtain desired chemical and physical properties. This gives RuNPs a wide range of multifunctionality. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] The synthesis of RuNPs by following the organometallic approach with [Ru(COD)(COT)] leads to the hydrogenation of the olefins to cyclooctane which present weak interactions with the RuNPs. As a consequence, the particles start to agglomerate and precipitates as bulk material at least in common solvent used in the RuNPs synthesis.

For example, tetrahydrofurane (THF) has been shown that although its coordination ability at metal surface, it does not allow the formation of homogeneous NPs, leading to aggregates. This phenomenon is even worse when using n-pentane due to its absence of metal interacting functional groups. However, it has been demonstrated that a combination of an alcohol like methanol with THF, allows the formation of small RuNPs. Alcohols bearing an alkyl chain longer than ethanol are also efficient stabilizers of RuNPs without any extra ligand. [START_REF] Pelzer | Organometallic Synthesis of Size-Controlled Polycrystalline Ruthenium Nanoparticles in the Presence of Alcohols[END_REF] In order to limit the agglomeration of the formed RuNPs, two different strategies have been developed. The first one implies the use of polymers as ligand barrier and the second is based on the addition of organic ligands than directly interact with the metal surface. Cellulose [START_REF] Duteil | Preparation of Organic Solutions or Solid Films of Small Particles of Ruthenium , Palladium , and Platinum from Organometallic Precursors in the Presence of Cellulose Derivatives[END_REF] and mainly polyvinylpyrrolidone (PVP) have been widely used to form RuNPs, these polymers Roberto González Gómez 48 avoid agglomeration of the particles by providing a poor interacting ligand barrier with the RuNPs surface. [START_REF] Koczkur | Polyvinylpyrrolidone (PVP) in nanoparticle synthesis[END_REF] On the other hand, organic ligands are very interesting stabilizers because they can modulate better their size and morphology due to its participation in the nucleation and growth processes during the NP synthesis. Given their different chemical nature, ligands offer a large variety of functional groups able to interact with the metal surface which will influence the growth of the particles, as well as the quantity of used ligand in the in-situ synthesis.

These variables can have different impact degrees on the RuNPs, depending on the systems either the size, dispersion, surface state or also organization of the particles. For example, RuNPs show smaller sizes when the electron donor strength of the ligand increase (figure 1.13). [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Figure 1.13 Variation of the size of RuNPs synthetized by the organometallic approach in relation with the ligand donor strength of the stabilizers. Ligands: 1,3-dicyclohexylimidazolium-2-di-p-tolylcarbodiimide; 1,3-dimethyl-4,5-diundecyl imidazol-2-ylidene; bis-(diphenylphosphino)butane, heptanol, respectively. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] In the last years, RuNPs have been widely synthetize through the organometallic approach by using different kind of ligands. The material reactivity was modulated and tested by changing the type of ligand used for its synthesis. Hereafter are enlisted some examples of the used ligands.

Roberto González Gómez 49

 Alcohols: heptanol, propanol [94]  Amines: hexadeclamine (HDA), octylamine [97]  Aminophosphines: 1,3,5-tri-aza-7-phosphaadamantane (PTA) [98]  Phosphines:

bis-(diphenylphosphino)butane (dppb) [99]  N-heterocycles carbenes (NHCs):

N,N-di(tert-butyl)imidazol-2- ylidene [100]
 Pyridines: 4-(3-phenylpropyl) pyridine [101] RuNPs are widely used as reference because it is possible to shed light on their chemical behavior and on their surface/structure properties due to the absence of magnetic perturbations, such as Knight shift. [START_REF] Novio | Location and Dynamics of CO Co-ordination on Ru Nanoparticles: A Solid State NMR Study[END_REF] At least at the range size of [1 -2 nm], [START_REF] Pelzer | New Ru Nanoparticles Stabilized by Organosilane Fragments[END_REF] which make the obtained RuNPs suitable to be characterized by solid and liquid NMR studies. ([104], [START_REF] Novio | Surface chemistry on small ruthenium nanoparticles: evidence for site selective reactions and influence of ligands[END_REF]) The almost absence of this phenomenon is highlighted when oxygen spacer are present in the interface of the formed hybrid material, such as hydroxyl group. [START_REF] Tedsree | Formate as a surface probe for ruthenium nanoparticles in solution 13C NMR spectroscopy[END_REF] As a result, it has been possible to detect mobile hydrogen species on RuNPs [START_REF] Schröder | Ruthenium nanoparticles inside porous [Zn4O(bdc)3] by hydrogenolysis of adsorbed [Ru(cod)(cot)]: A solid-state reference system for surfactant-stabilized ruthenium colloids[END_REF] and even get a clear evidence of the interaction between ligands such as phosphines [START_REF] González-Gálvez | Phosphine-Stabilized Ruthenium Nanoparticles: The Effect of the Nature of the Ligand in Catalysis[END_REF] or carbenes [START_REF] Lara | Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity[END_REF] with the metal surface. The last findings have opened a new branch for studying the influence of the ligands onto the RuNPs in order to change their reactivity and selectivity in several catalytic reactions.

In the frame of the present work, it was stablished to use different carboxylic acid as ligands to stabilize RuNPs which to our knowledge have not been deeply yet studied. In the literature, is recently reported only one attempt to create RuNPs with organometallic chemistry tools by using hexasubstitued fullerene (C 66 (COOH) 12 ) as stabilizing agent. [START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF]

Experimental and Theoretical Characterization of RuNPs

Ligand-stabilized RuNPs are hybrid materials that possess a metal core and an organic layer made of ligands capping the metal surface. Since the interaction between metal core and ligands in NPs can be strong, it is difficult to characterize them experimentally, e.g. NMR or IRFT, due to the low mobility of the organic layer. [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF] Roberto González Gómez 50

Therefore, a trustworthy RuNP theoretical model is highly desired in order to describe a synthetized nanosystem, aiming to understand its activity and selectivity properties for a target catalytic reaction for instance. Especially, the relationships between the metal core and the coordinated species in terms of steric and electronic effects are required in order to be able to adjust the synthesis conditions for reaching identified properties. Taking into account the QSE and the degeneracy of the electronic states at the Fermi level, a good approach to modelling the RuNPs is based on periodic-DFT methodologies. [START_REF] Gerber | Nanomaterials in Catalysis[END_REF] Combining theoretical and experimental tools has been already validated as a powerful approach to describe the electronic structure of MNPs and also the interactions of the metal surface with the capping ligands. Some examples of the findings obtained by the combination of these approaches are enlisted below. ( [113], [114])

 Surface composition of RuNPs in equilibrium with syngas.

[82]

 Enantiospecific CH activation using ruthenium catalyst corroborated by the Ru 55 model. [START_REF] Taglang | Enantiospecific C-H Activation Using Ruthenium Nanocatalysts[END_REF] It is possible to establish a fruitful dialog between theory and experiments thanks to a combination of MNPs characterization methods. In this way, the nanosystems can be better described in terms of structure, composition, catalytic activity and selectivity, due to the wider vision that these joint approaches can provide. In the following

Modification of RuNPs by Ligand Exchange

MNPs multifunctionality can be improved by changing their size, morphology and their capping ligands. All of these characteristics are intrinsically related and determine the stability, activity and selectivity of the nanosystem. ([13], [START_REF] Fedlheim | Metal nanoparticles: synthesis, characterization and applications[END_REF]) Initially, MNPs characteristics were modified by changing their synthetic conditions but it is also possible to tune them by modifying preformed nanosystems.

For instance, the stability of MNPs can be improved by exchanging the molecules laying on their surface with the aim to provide new properties and functionality to the MNPs. [START_REF] Woehrle | Thiol-functionalized, 1.5-nm gold nanoparticles through ligand exchange reactions: Scope and mechanism of ligand exchange[END_REF] In almost all cases, the exchanged ligand has lesser interaction with the metal surface than the new capped Roberto González Gómez 52 ligands. Meaning that a necessary condition to have an efficient ligand exchange is to add a stabilizing agent that will stronger bound to the MNPs surface (figure 1.14). [START_REF] Hurst | N-Heterocyclic carbene coated metal nanoparticles[END_REF] Figure 1.14 Representation of ligand exchange at the surface of MNPs.

For noble metals, it has been reported that thiol derivatives have a high affinity for MNPs surface making them suitable compounds to be incorporated onto the nanosystem, e.g.

alkanethiolates for chelating thiols. [START_REF] Love | Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology[END_REF] Nevertheless, it is important to point out that the ligand exchange leads to another type of MNPs stabilization. Therefore, the size, shape, composition and surface-state of the nanoparticles can be modified. [START_REF] Brown | Controlled Growth of Gold Nanoparticles during Ligand Exchange[END_REF] Ligand exchange is often applied for changing the chemical and physical properties of preformed nanoparticles. Since MNPs are usually synthetized in organic solvents, it could be necessary to make them soluble in water by a phase transfer. [START_REF] Palma | Silane ligand exchange to make hydrophobic superparamagnetic nanoparticles water-dispersible[END_REF] This can be obtained by making a ligand exchange between hydrophobic and hydrophilic ligands or vice versa (figure 1.15). ([121], [START_REF] Branca | Water Transfer of Hydrophobic Nanoparticles: Principles and Methods[END_REF]) This methodology is often followed for increasing the MNPs biocompatibility, [START_REF] Nikolic | Tailor-Made Ligands for Biocompatible Nanoparticles[END_REF] however it can be also used for applications in catalysis in neat water or in biphasic conditions.

Roberto González Gómez 53

Figure 1.15 Some hydrophobic and hydrophilic capping ligands used for MNPs phase transfer. [START_REF] Sperling | Surface modification, functionalization and bioconjugation of colloidal inorganic nanoparticles[END_REF] This methodology can be also applied for the identification of the real nature and composition of a stabilizing agent onto RuNPs. [START_REF] Favier | Palladium and ruthenium nanoparticles: Reactivity and coordination at the metallic surface[END_REF] By taking into account the ligand bond strength, it is possible to remove ligands from the surface of preformed RuNPs and replace it by dodecanethiol. In this way, the RuNPs get poisoned and the exchanged ligand can be characterized. [START_REF] Escárcega-Bobadilla | Ruthenium and rhodium nanoparticles as catalytic precursors in supercritical carbon dioxide[END_REF] It is well-known that the hydrogenation of benzene under reductive atmosphere cannot be afforded in normal conditions and it is necessary the use of a catalyst. [START_REF] Schoenmaker-Stolk | The catalytic hydrogenation of benzene over supported metal catalysts: I. Gas-phase hydrogenation of benzene over ruthenium-on-silica[END_REF] Ruthenium-based catalysts have been widely used for the olefin or arenes reductions and its potentiality has increase when RuNPs is used. Indeed, the presence of hydrogen atmosphere and RuNPs is favorable to the hydrogenation of these functions present in the skeleton of the ligands. [START_REF] Roucoux | Reduced transition metal colloids: a novel family of reusable catalysts?[END_REF] Therefore, the use of ligand exchange is a strategy to circumvent this issue and insert alkyne-or aryl-based ligands onto RuNPs. ([127], [START_REF] Zhang | Alkyne-Functionalized Ruthenium Nanoparticles: Impact of Metal-Ligand Interfacial Bonding Interactions on the Selective Hydrogenation of Styrene[END_REF])

In the present work, the technique of ligand exchange was applied as approach in order to introduce carboxylic acids containing aryl substituents onto the issued RuNPs by avoiding their hydrogenation. The main perspective was to insert polypyridyl based photosensitizers (PS) having carboxylic acids as pending groups to anchor them at the surface of preformed RuNPs and obtain hybrid nanomaterials PS-RuNPs.

CHAPTER I

RuNPs in Catalysis

Roberto González Gómez 54

Interest of RuNPs in Catalysis

A crucial role for the industry progress has been the development of novel highly active and selective catalysts. [START_REF] Serp | Nanomaterials in Catalysis[END_REF] During the last decades, catalysts have been the center of attention of many research institutes in order to improve or develop novel heterogenous or homogeneous catalyst. Concerning MNPs they have also attracted a lot of interest from the scientific community owing they combine advantages both from homogeneous and heterogeneous catalyst, such as active surface and electronic configuration, which make them very efficient catalysts in certain catalytic processes. [START_REF] Gonzalez-Galvez | NHC-stabilized ruthenium nanoparticles as new catalysts for the hydrogenation of aromatics[END_REF] Some authors even point out that MNPs possesses the best catalytic efficiency. [START_REF] Astruc | Nanoparticles and catalysis[END_REF] RuNPs have shown high catalytic activity for hydrogenation reactions such as selective reduction of olefins, arenes hydrogenation, etc., under mild conditions. [START_REF] Rossi | Ruthenium nanoparticles prepared from ruthenium dioxide precursor: Highly active catalyst for hydrogenation of arenes under mild conditions[END_REF] Aromatic ring reduction was obtained in the presence of RuNPs stabilized by diphosphites [START_REF]Diphosphite ligands derived from carbohydrates as stabilizers for ruthenium nanoparticles: promising catalytic systems in arene hydrogenation[END_REF] , however the efficiency of RuNPs was improved when the particles were stabilized by carbenes. [START_REF] Gonzalez-Galvez | NHC-stabilized ruthenium nanoparticles as new catalysts for the hydrogenation of aromatics[END_REF] These studies evidenced the influence of the stabilizing agent into the catalytic properties of RuNPs.

For similar aryl reductive reaction, it was observed that the RuNPs size has also a direct effect on the catalytic performance. [START_REF] González-Gálvez | Phosphine-Stabilized Ruthenium Nanoparticles: The Effect of the Nature of the Ligand in Catalysis[END_REF] By changing the quantity of stabilizing agent introduced during the NPs synthesis, it was possible to change the size of the particles and also their catalytic

properties. [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF] The selectivity of the RuNPs for the reduction of styrene has been evaluated according to free active sites located onto their surface and their size. [START_REF] Novio | Surface chemistry on small ruthenium nanoparticles: evidence for site selective reactions and influence of ligands[END_REF] For the aromatic ring reduction it is necessary to have enough free space at the surface of RuNPs. It is generally considered that a minimum of 3 neighboring ruthenium atoms is required to enable reduction an aromatic group, meaning it can be done only on faces. Meanwhile, alkenes can be reduced in the edges or corners of the RuNPs (figure 1.16). [START_REF] Bonne | Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction[END_REF] CHAPTER I

RuNPs in Catalysis

Roberto González Gómez 55 There are many other catalytic reactions that can be performed by using RuNPs. Among them, it can be found the hydrogenation of carbon monoxide (CO) into alkanes for the Fisher-Tropsch Synthesis (FTS). [START_REF] Martinez-Prieto | Organometallic ruthenium nanoparticles as model catalysts for CO hydrogenation: A nuclear magnetic resonance and ambient-pressure X-ray photoelectron spectroscopy study[END_REF] In the other hand, RuNPs have also demonstrated to be efficient catalysts for the oxidation of CO into carbon dioxide (CO 2 ). [START_REF] Joo | Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide Oxidation[END_REF] In this context, it was observed that not only the size and type of capping ligand affect the catalytic performance, but also their morphology and crystalline structure. [START_REF] Kusada | Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction Method[END_REF] RuNPs are also active systems in photocatalysis or electrocatalysis. [START_REF] Drouet | A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions[END_REF] Recently, studies were published concerning the use of RuNPs prepared by the organometallic approach for the catalytic HER reaction which is involved in the water splitting process. [START_REF] Creus | Ruthenium Nanoparticles Supported onto Carbon Microfibers for Hydrogen Evolution Electrocatalysis[END_REF] In particular, it was found that RuNPs catalysts show a higher performance than ruthenium black powder, as it has been shown for ruthenium nanosystems functionalized by 4-phenylpyridine ligands. In fact, the latter presents an electrocatalytic activity close to that of platinum based catalysts, which are reported to be the most efficient catalysts for this reaction. [START_REF] Creus | Ruthenium Nanoparticles Supported onto Carbon Microfibers for Hydrogen Evolution Electrocatalysis[END_REF] This again underlines the strong role of the stabilizing ligand onto NPs properties and reinforces the idea to develop fine comparative studies in order to identify better performing systems for a target reaction.

As it will be described later on, this PhD manuscript lies in this context. It is focused on the synthesis and the full characterization (experimentally and theoretically) of RuNPs stabilized with carboxylic acids. These RuNPs were chosen to serve as models for the future design of efficient Roberto González Gómez 56 nanocatalysts for water splitting process. This reaction can be electro-or photo-activated, this last mechanism requires to associate a photosensitizing species to the RuNPs which can be performed through the anchoring a polypyridyl ruthenium complex at the surface of the particles by grafting pending groups, like carboxylic acids.

Introduction

Roberto González Gómez 59

Introduction

Science is in continuous evolution and Chemistry is not the exception, in the last years new branches were explored. The ability to create, characterize and control artificial structures in a nanometer (nm) size range is one of the examples, so-called nanoscale science or nanotechnology.

The manipulation of different systems at a nanometer level and its applications, involves the cooperative efforts of many sciences such as molecular biology, physics, materials science, chemistry, etc.

The human necessity to create new materials with novel or improved properties as thermal conductivity, optical response, elasticity, etc., is the driving force to develop nanomaterials. In fact, these materials such as metal nanoparticles (MNPs) present changes in the electronic, chemical and physical properties in comparison with bulk materials or molecular compounds. Also, this branch of materials science has been developed in order to perform more efficient and complex demands like catalysis for the decomposition of contaminants, response-materials with higher sensitive to a specific stimulus, devices for conversion of sunlight into current and even energy storage systems.

Materials build in the nanometer range (figure 2.1) are described as nanocomposites which are performed as continuous assembled objects, molecules or atoms till they arrive to a nanosize. Their novel behavior implies the combination of their individual components properties and their mutual interactions. [138] Therefore nanoscale materials show a behavior intermediate between bulk material and molecular systems.

Introduction

Roberto González Gómez 60 [139]

The fraction of atoms that are present at the surface of the nanomaterials, [80.0 -50.0 %] for MNPs ranging from [1.0 -2.0 nm], is quite bigger than the possible reactive atoms present in a bulk material. Therefore, the nanosystems possess improvement properties, like higher reactivity than the corresponding macro materials did not possess.

Manipulation of materials at the nanometer scale produce nanoparticles and nanostructures with different sizes, morphologies and structures. The nanomaterials have a length size typically between [1.0 -100.0 nm] at least in one dimension. The size of them are smaller than bulk materials but higher than small molecules. [START_REF] Sau | Complex-shaped metal nanoparticles: bottom-up syntheses and applications[END_REF] For example, palladium nanoparticles in size between ca. [1 -2 nm] possess a number of particles ranging between [35 -290 atoms], meanwhile for ruthenium nanoparticles (RuNPs) it ranges from ca. [38 -310 atoms] at the same NP size in their typically crystalline structure (table 2.1). [START_REF] Hosseini-Monfared | Dioxygen oxidation of 1-phenylethanol with gold nanoparticles and N-hydroxyphthalimide in ionic liquid[END_REF] Table 2.1 Number of atoms for metal nanoparticle of 1.0 and 2.0 nm in size following their typical crystalline structure.

Ru

Introduction

Roberto González Gómez 61

Nanoparticles size is quite important because at certain length the nanomaterials follow quantum mechanical rules instead of the classic. This phenomenon is found as a result of their electronic compatibility with atoms or molecules.

The fundamental properties of metal nanoparticles depend on their size, morphology, shape (anisotropy), structure, crystallinity, etc. Thus, these materials can be tune in order to find novel properties by changing the synthesis conditions. It has been reported that drastic changes can be observed if small modifications on the nanoparticles morphology are created. Therefore, it is of highly importance to obtain monodisperse nanoparticles. Indeed for this reason, a synthetic procedure which can provide controlled nanosystems is desired. [START_REF] Schmid | Conclusions and Prespectives[END_REF] Different strategies have been developed in order to build controlled nanoparticles, mainly including protective ligand shells such as organic molecules. Amines, phosphines, thiols and oligomers have been widely used to synthetize MNPs. These moieties do not control just the nanoparticles growthless and morphology, but also changes their solubility. [START_REF] Wang | Water-soluble Fe3O4nanoparticles with high solubility for removal of heavy-metal ions from waste water[END_REF] Despite of the flourishing stapes of nanoscience in the early years of this century, the interest in metal nanoparticles (MNPs) continues to be very strong in both academic and industrial domains due to their several applications in many fields ranging from biology, [START_REF] Howes | Colloidal nanoparticles as advanced biological sensors[END_REF] medicine, [START_REF] Murthy | Nanoparticles in modern medicine: state of the art and future challenges[END_REF] catalysis, [START_REF] Palomo | Biosynthesis of Metal Nanoparticles: Novel Efficient Heterogeneous Nanocatalysts[END_REF] optoelectronics, [START_REF] Yoon | Surface modifications and optoelectronic characterization of TiO2-nanoparticles: Design of new photo-electronic materials[END_REF] to energy [START_REF] Serrano | Nanotechnology for sustainable energy[END_REF] (figure 2.2).

Figure 2.2 Interest on metal nanoparticles in different fields: (a) medicine; [START_REF] Murthy | Nanoparticles in modern medicine: state of the art and future challenges[END_REF] (b) catalysis; [START_REF] Palomo | Biosynthesis of Metal Nanoparticles: Novel Efficient Heterogeneous Nanocatalysts[END_REF] (c) biology. [START_REF] Howes | Colloidal nanoparticles as advanced biological sensors[END_REF] Introduction Roberto González Gómez 62

A bottom-up synthetic methodology that can provide controlled nanoparticles with homogenous morphology and avoiding the presence of undesired reactions substrates is the organometallic approach. [START_REF] Amiens | Controlled metal nanostructures: Fertile ground for coordination chemists[END_REF] This powerful methodology allows the formation of hybrid nanoparticles constituted of a metal core surrounded by an organic layer from metal-organic complexes as metal sources and polymers or ligands as stabilizing agents (figure 2.3). Together with the coordinating character of the stabilizer, reductive agents used and applied reaction conditions for the decomposition of metal complexes are very important parameters to produce well-controlled zero-valent metal nanoparticles. Thermodynamic and kinetic parameters highly influence the decomposition and growth process, being thus key-points to get precisely controlled NPs in terms of size, shape, composition, surface state and dispersion. This approach provides MNPs which possess a clean surface due to the practical easy removal of side reaction products such as alkanes, but since they are stabilized by molecules covalently bounded (organic stabilizers), their surface composition is also a key factor that influences the electronic structure of the metal core.

Therefore, in this approach the surface ligands nature can be also tuned to provide different self-assembly properties. Thus, the nanoparticle properties can be adjusted by changing the stabilizing agent and/or the metal source, having even a high impact in their nanosystems solubility.

Introduction

Roberto González Gómez 63

MNPs have been produced by several research groups but due to its fascinating applications there is still a need to modify their surface in order to improve their properties and extend their multifunctionality.

As mentioned in the previous chapter, the organometallic approach has been largely employed to produce metal ruthenium nanoparticles (RuNPs). For this purpose, various ligands such as amines, pyridines, imines, phosphines, carbenes, alcohols, thiols, betaines, etc., have been used as stabilizing agents ([59], [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF], [START_REF] Favier | A new and specific mode of stabilization of metallic nanoparticles w[END_REF], [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF]) (figure 2.4 a). However, carboxylic acids have received much less attention because they are identified as proton sources [START_REF] Grasemann | Environmental Science Formic acid as a hydrogen source -recent developments and future trends[END_REF] (figure 2.4 b) even when their adsorption on several metallic surfaces has been broadly observed and studied. [START_REF] Mars | The catalytic decomposition of formic acid[END_REF] But the use of simple carboxylic acids can be of interest in order to study the anchoring at a metal surface of more sophisticated molecules having carboxylic pending groups like polypyridyl ruthenium complexes that are used in the water-splitting reaction activated by light for example. ref [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] (b) reaction pathways for the formic acid decomposition. [START_REF] Grasemann | Environmental Science Formic acid as a hydrogen source -recent developments and future trends[END_REF] To our best knowledge the literature reports only one attempt on the stabilization of RuNPs with carboxylic acids following the one-step organometallic approach, using fullerenehexamalonic acid (C 66 (COOH) 12 ) as stabilizer (figure 2.5). [START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF] Introduction Roberto González Gómez 64 ) y nanoparticles. [START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF] In this chapter, it is going to be presented a full-study where computational and experimental chemistry team-up and complement each other, in order to completely characterize ruthenium nanoparticles (RuNPs) functionalized at their surface by ethanoic acid molecules (Ru x (CH 3 COOH) y ). This carboxylic acid has been chosen to build a model system due to the simplicity of the acid that allows more accessible theoretical calculations. It was nevertheless necessary to first evaluate the potential of this ligand as RuNPs stabilizer.

As a result of the characterization, a better understanding of the NPs electronic structure and their surface properties will be shown. The combined strategy offers new data about the 3D representation of ultra-small RuNPs, this methodology offered valuable information on the surface chemistry of the nanoparticles, giving a balance between their surface coverage and ligand adsorption energies. By this way, potential interests of the studied particles can be drawn for catalytic application such as HER.

It is important to remark that before performing any theoretical investigation, it is necessary to have a structural model not beyond the reach of the first principle methods which is as close as possible to experimental findings (figure 2.6). [START_REF] Häkkinen | Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts[END_REF] This is with the aim to calculate reliable physical or chemical properties, however this goal is not easy to reach and even more complicated when it concerns hybrid and complex systems such as metal nanoparticles.

Introduction

Roberto González Gómez 65 ) and their different coordination modes. [START_REF] Häkkinen | Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts[END_REF] Yet, with the appropriated tools in hand, it is possible to use computational chemistry with the same level of accuracy and relevance as in molecular chemistry in order to describe ultra-small nanoparticles. This PhD work took benefit of previous results obtained. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] Thus, the following section will describe the synthesis of RuNPs stabilized with ethanoic acid (CH 3 COOH) and their full characterization using several techniques namely, transmission electron microscopy (TEM), high-resolution TEM (HRTEM), wide-angle X-ray scattering (WAXS), proton and 13-carbon nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR).

These techniques were used in order to get experimental information on the RuNPs morphology (size, shape & crystalline structure) and the composition-surface state (nature and coordination of surface molecules) of the obtained RuNPs. The spectroscopic experimental assignations were corroborated in parallel with DFT calculations of the vibrational normal modes obtained from the optimized RuNPs as well as the chemical shifts found for different carboxylic coordination modes onto a hexanuclear ruthenium cluster [Ru 6 ].

The surface ligand coverage of these novel RuNPs was also investigated and discussed both experimentally and theoretically with the aim to describe the ruthenium nanoparticle surface chemistry. The RuNPs surface state were obtained with atomic charges and d-band centers calculations.

Introduction

Roberto González Gómez 66

Furthermore, to understand the RuNPs catalytic properties and their possible performance, it was obtained the ligand adsorption energy onto optimize RuNPs. These are fundamental calculations for implement the Sabatier-Balding principle and the Brønsted-Evans-Polanyi (BEP) relations. [START_REF] Chorkendorff | Surface Reactivity[END_REF] Also in this chapter, the RuNPs catalytic efficiency was evaluated for the hydrogen evolution reaction (HER) due to its relationship between the nanoparticles surface composition and the molecular hydrogen (H 2 ) dissociative adsorption energies. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF]

Synthesis and Structural Characterization of RuNPs

The ruthenium nanoparticles (RuNPs) presented in this chapter were synthetized at room temperature (r.t.) by following the organometallic approach (scheme 2.1). Where a ruthenium organometallic precursor ([Ru(COD)(COT)]; (COD= 1,5 cyclooctadiene, COT= 1,3,5cyclooctatriene)) was reduced in a pentane solution under molecular hydrogen (H 2 ) and in the presence of ethanoic acid as stabilizing agent (see section 6.1.2.2).

Scheme 2.1 General synthesis pathway of NPs by following the organometallic approach.

Organometallic Ruthenium Precursor

The source of ruthenium metal to synthetize RuNPs could come from different organometallic precursors. Some of them such as [RuCl 3 ] and [Ru(NO)(NO 3 )] contains halogens or oxides that can directly interact with the nanoparticles surface, providing a polluted surface. For this reason, is desired to find an organometallic precursor that, when decomposed in a reductive Roberto González Gómez 67 atmosphere, has secondary substrates molecules unable to interact with the nanoparticle surface.

For that purpose, the synthesis of ruthenium nanoparticles was performed by using [Ru(COD)(COT)] as metal source.

[Ru(COD)(COT)] is a yellowish crystalline material that was synthetized and characterized according to a published procedure [START_REF] Porri | A New Synthetic Method for the Preparation of Cyclo-olefin Ruthenium Complexes[END_REF] (see section 6.1.2.1). This metal precursor was used for the first time in the 80's decade, when it was exposed to a reductive atmosphere of hydrogen (H 2 ) in the presence of different phosphines (scheme 2.2). [START_REF] Chaudret | The use of (cyclo-octadiene)(cyclo-octatriene) ruthenium (0) as the starting material for the synthesis of mono-and poly-nuclear ruthenium polyhydride phosphine complexes[END_REF] Scheme 2.2 Reactions profile of [Ru(COD)(COT)] with various types of phosphines. [START_REF] Chaudret | The use of (cyclo-octadiene)(cyclo-octatriene) ruthenium (0) as the starting material for the synthesis of mono-and poly-nuclear ruthenium polyhydride phosphine complexes[END_REF] Later, it was found that the double bonds of the cyclooctatrien (COT) can be easily displaced by small cone angle phosphines ligands. After, it was found that the [Ru(COD)(COT)]

substituents can be easily removed by the presence of molecular hydrogen. In general, the reduction reaction possesses fast kinetics and, in the absence of any strong coordinated ligand, all the double bonds are reduced forming naked ruthenium atoms, that start to nucleate and coalescence in order to reduce their surface energy. [START_REF] Kraynov | Concepts for the stabilization of metal nanoparticles in ionic liquids[END_REF] The previous observations have provided the possibility to prepare RuNPs by decomposing the [Ru(COD)(COT)] in the presence of hydrogen. Considering, as main factor, the addition of a coordinated ligand that prevent the excessive growth of the particles and the formation of RuNPs, avoiding the generation of a bulk metal material.

Roberto González Gómez 68

This methodology has been applied for more than 30 years and therefore several types of ligands have been used as stabilizing agents to form RuNPs. Polymers, [START_REF] Duteil | Preparation of Organic Solutions or Solid Films of Small Particles of Ruthenium , Palladium , and Platinum from Organometallic Precursors in the Presence of Cellulose Derivatives[END_REF] weakly [START_REF] Vidoni | Novel, Spongelike Ruthenium Particles of Controllable Size Stabilized Only by Organic Solvents[END_REF] or strong coordinated ligands [START_REF] Martinez-Prieto | Organometallic ruthenium nanoparticles as model catalysts for CO hydrogenation: A nuclear magnetic resonance and ambient-pressure X-ray photoelectron spectroscopy study[END_REF] have been utilized to create a wide gamma of RuNPs of different sizes and morphologies, which possesses different physical and chemical properties.

Synthesis of Ethanoic Acid-Capped RuNPs

As a first attempt to prepare monometallic RuNPs using ethanoic acid as stabilizing agent, a [Ligand]/[Ru] ratio of 0.2 molar equivalent (equiv.) compared to the quantity of the ruthenium precursor introduced was used (Ru X (CH 3 COOH) 0.2 ). This proportion of ligand was chosen as starting point because it was previously proved to be effective to generate stable and homogenous RuNPs with different ligands. [START_REF] Roucoux | Rhodium and Ruthenium Nanoparticles in Catalysis[END_REF] More precisely, [Ru(COD)(COT] and ethanoic acid (0.2 equiv.) were dissolved in pentane under argon atmosphere inside a Fisher-Porter reactor, forming a yellowish solution. The reactor was evacuated under high-vacuum and then pressurized with molecular hydrogen (3 bar) under vigorous stirring at r.t. After ca. 2 minutes, the initial yellow solution turned black. To ensure complete decomposition of the ruthenium organometallic precursor, the reaction mixture was maintained for 30 min (scheme 2.3). Then, the reactor was evacuated under high-vacuum in order to remove the reductive gas excess and the colloidal suspension was concentrated to the half volume.

During the synthetic process a stable colloidal solution was not achieved, indeed, the formation of a precipitate was observed after ca. 10 min of reaction.

Roberto González Gómez 69 Roberto González Gómez 70 The EDX analysis for the element quantification was performed for the highlighted spots, on them, it was possible to observe the relation between the oxygen and ruthenium amount found in the sample (table 2.2). This ratio indicates that the spot 001, which has a high concentration of RuNPs, has less quantity of oxygen (ca. 0.2) than the expected from the experimental conditions used for the RuNPs synthesis, [O]/[Ru] = 0.4. This result indicates that no oxidation took place and that lower quantity of the 0.2 equiv. of ethanoic acid added for the NPs synthesis is interacting with the nanosystem. Also, it was determined that the RuNPs surrounding area (spot 002) possesses low quantity of ruthenium, which could explain the heterogeneity found in the system.

Roberto González Gómez 72 Due to the formation of small RuNPs, it is possible to formulate as a hypothesis that the ethanoic acid can act as a ligand to stabilize RuNPs. However, the lack of homogeneity and stability of the sample obtained could be attributed to a deficiency of capping ligand. Consequently, it was considered to use more ethanoic acid ligand. In these synthesis conditions, the yellowish initial solution, formed by the dissolution of the [Ru(COD)(COT)] and ethanoic acid in pentane, turned black at the same reaction time as previously observed for Ru x (CH 3 COOH) 0.2 (ca. 2 min), but this time no precipitate was observed under vigorous stirring. However, a semi-stable colloidal solution was obtained since metal product sedimentation appeared when magnetic stirring was stopped for a few hours.

Structural

This deposition can be due to a low solubility of the nanoparticles in pentane. Primally, this phenomenon can be explained by the fact that ethanoic acid contains a polar head that can interact with the surface of the RuNPs and a short organic tail thus making the RuNPs less soluble in pentane. [START_REF] Li | Double-responsive polyampholyte as a nanoparticle stabilizer : application to reversible dispersion of gold nanoparticles[END_REF] Stirring again the sample allowed to get a colloidal suspension that can be better analyzed.

Roberto González Gómez 73 As it can be seen from TEM analysis, the increase of ethanoic acid quantity to a [CH 3 COOH]/[Ru] of 0.4 equiv. led to a stable colloidal suspension containing small, semi-homogeneous and well-dispersed RuNPs. Thus, confirming the previous hypothesis planted concerning the use of ethanoic acid as stabilizing agent for forming RuNPs was proved to be true CHAPTER II

Synthesis and Structural Characterization

Roberto González Gómez 74 by increasing the ligand metal ratio. Given the stability and homogeneity of Ru x (CH 3 COOH) 0.4 system, it was decided to focus on it for the rest of this theoretical and experimental study on ethanoic acid-capped RuNPs.

HRTEM studies performed using the same grid as for TEM analysis, the studio revealed RuNPs with poor crystallinity but higher than that of the Ru x (CH 3 COOH) 0.2 system (figure 2.11 a).

Despite of this factor, some atomic planes were sufficiently visible to be measured to resolve their Wide-angle X-ray Scattering (WAXS) is a useful technique to get information on the crystalline structure and size of crystalline domains of small NPs (< 4 nm), data that can be compared to those obtained by TEM and HRTEM. It is worth to point out that WAXS is a statistical technique quite sensitive for small and ultra-small objects no matter the oxidation state or crystallinity.

Roberto González Gómez 75

WAXS data was recorded on sample Ru x (CH 3 COOH) 0.4 in the solid state under argon atmosphere (inside a sealed capillary). The results did not evidence any crystalline feature for the Ru x (CH 3 COOH) 0.4 . Besides a huge peak at low angle indicative of agglomeration, only very broad features were observed which are not in agreement with any compact structure (figure 2.12 a).

In the RDF pattern in real space (Fig. 2.12 b), it is observed a well-defined function fully consistent with metallic ruthenium, which is poorly resolved and does not allow a clear structure indexation. A coherence length, which corresponds to the size of crystalline domains, can be estimated to ca. 0.9 nm. This pattern points to very small amorphous metallic RuNPs. The comparison of WAXS and HRTEM data evidenced at first approximation some discrepancy but they are not in contradiction since WAXS is a statistic technique sensitive to very small objects, crystalline or not, whilst HRTEM largely relies on phase contrast and emphasizes the better crystallized fraction of a sample. Indeed, the WAXS RDF indicates an estimated RuNPs coherence length smaller than that of TEM by ca. 0.6 nm. Revealing the probable presence of ultra-small nanoparticles or nanoclusters, smaller than < 1.0 nm which are difficult to characterize by HRTEM. One can thus estimate that the hcp NPs revealed by HRTEM are likely related to a limited coalescence leading to bigger domains. [START_REF] Liakakos | The Big Impact of a Small Detail: Cobalt Nanocrystal Polymorphism as a Result of Precursor Addition Rate during Stock Solution Preparation[END_REF] Also, WAXS analysis provides useful information about the stability of metal nanoparticles under inert atmosphere with time. Two different measurements have been performed on the same sealed capillary of Ru x (CH 3 COOH) 0.4 (thus RuNPs kept under argon atmosphere) with a delay time of more than one year between them (figure 2.13). As it can be seen, no modifications were Roberto González Gómez 76 observed between both measurements, meaning that at least without reductive or oxidative atmosphere, the general structure and composition of the ruthenium particles remained. In addition, it can be seen that the NPs surrounding zone has no metal presence (spot 004), this result is quite different than that obtained for Ru x (CH 3 COOH) 0.2 NPs where some leftover ruthenium was found in the similar spot (figure 2.14 b). As a brief conclusion, it can be said that for Ru x (CH 3 COOH) 0.4 NPs system all the metal precursor supplied for the synthesis was decomposed into a semi-homogeneous ruthenium nanostructures, which possess high-sensitivity to the electron beam. This data is another evidence of the importance of the nanoparticles synthesis conditions, as for this study case, the relevance of the quantity of ligand used to stabilize the RuNPs.

Roberto González Gómez 77 Meanwhile, for the 005 spot it was ca. 0.5, being this value lower than the expected from the experimental ratio conditions (0.8). Even when this technique is not well-known as a quantitative methodology, it can be said that there is a lower quantity of ligand surrounding the NPs than the added into the synthesis setup, this phenomenon can be attributed to the ligand lost in the washing process. Another observable fact is that no nanoparticles oxidation took place, meaning that as it was seen in WAXS, the RuNPs are stable through time and yet probably in different atmospheres.

Study of the Ethanoic Acid Interactions with the

Surface of RuNPs

Complementary techniques based on nuclear magnetic resonance (NMR) spectroscopy were performed in order to study the interaction strength of ethanoic acid at the surface of RuNPs. In parallel, DFT calculations were carried out to provide theoretical information on the chemical shifts depending on the coordination mode of the ethanoic acid at the particle surface by using a hexanuclear ruthenium cluster [Ru 6 ] as a model system.

This will be an important step to analyze the surface state of the nanosystem and to prove the formation of a hybrid material. Besides, it will be the first time that the combination of theoretical and experimental results will be presented.

Proton-Liquid NMR Characterization

Small RuNPs are suitable nanomaterials to be analyzed by nuclear magnetic resonance, because they do not present a Knight shift phenomenon or if it is present is considered to be not significant. ([102], [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF]) This effect is correlated to a NMR signal displacement due to an additional magnetic field created by an electron cloud as present in metallic systems. [START_REF] Lynch | An overview of first-principles calculations of NMR parameters for paramagnetic materials[END_REF] Roberto González Gómez 79

Therefore, a proton-liquid NMR (

Roberto González Gómez 80

Previous statement is based on reports saying that molecules which have a high degree of freedom (like free CH 3 COOH) present sharper signals than rigid compounds. Ligands attached at the nanoparticles surface can thus be expected to have reduced dynamics and therefore to present broad signals. Presence of this type of peaks is often used as a proof or evidence of ligand coordination at the NPs surface. ([163], [START_REF] Liu | Determination of monolayer-protected gold nanoparticle ligand-shell morphology using NMR[END_REF])

In the present case, due to its signal position at ca. 2.08 ppm and broadness, this lightly shifted signal compared to that of free CH 3 COOH can be assumed to correspond to a methyl group close to the surface of the RuNPs coming from ethanoic acid. Thus, it is a direct prove of their interaction and their role in the RuNPs stabilization.

The assignation of this broad signal was confirmed by DFT calculations, where chemical shift of protonated-unprotonated carboxylic acid were calculated as free ligands and as interacting species in several coordination modes and locations onto a hexaruthenium nanocluster [Ru 6 ] (figure 2.16) by using Gaussian09 software. This strategy to obtain theoretical NMR chemical shifts was previously validated by different research groups (see section 6.2.5). ([165], [START_REF] Del Rosal | Ligand effect on the NMR , vibrational and structural properties of tetra-and hexanuclear ruthenium hydrido clusters : a theoretical investigation[END_REF]) As starting point, the mean chemical shift of the methyl protons of the free ligand species that could interact with the NP (carboxylic acid-carboxylate) was calculated. For the ethanoic acid dimer, the chemical shift was found to be at 1.9 ppm (figure 2.17 a), meanwhile this value changed to 1.3 ppm for the unprotonated ethanoate moiety (figure 2.17 b).

Roberto González Gómez 81 As it can be seen, the calculated methyl proton signal of the free ethanoic acid dimer is quite similar to that of the experimental counterpart (1.93 Furthermore, to corroborate this data some calculations were performed on small cations (Na + ) instead of the [Ru 6 ] nanocluster. First of all, as it was shown the ethanoate protons are shielded by ca. 0.6 ppm in comparison with that of the ethanoic acid dimer, due to a delocalized charge formed in the system. However, the interaction of the negative moiety with the ruthenium cluster deshields the methyl protons by a similar quantity of ppm (ca. [0.7 -0.9 ppm]). This assertion was supported by calculations performed in sodium ethanoate (CH 3 COONa), where the ethanoates protons are found to be at ca. 1.9 ppm with a deshielding of ca. 0.6 ppm.

As a result, it has been observed a counterbalanced phenomenon, that is why the methyl protons of the ethanoate moiety in interaction with the nanocluster seems to have similar chemical shift than that of the free ethanoic acid dimer. The level of deshielding caused by the metal interaction depends on its nature. For example, calculations performed with another cation The theoretical and experimental findings are summarized in the figure 2.21. Where it can be seen that signals visible for the free ethanoic acid experimental spectrum (blue) do not correspond to that of the Ru x (CH 3 COOH) 0.4 NPs system (red), meaning that there is no free ligand.

Given the DFT calculations, preliminary hypothesis can be done about the ligand features (ethanoate) and its coordination mode (bidentate). This is the first evidence of the mutual support Roberto González Gómez 84 importance between experimental findings and theoretical calculations for this complex system of RuNPs. The characterization of the Ru x (CH 3 COOH) 0.4 NPs was pursued with DOSY NMR studies.

Diffusion-Ordered Proton NMR Experiments

Diffusion-ordered NMR spectroscopy (DOSY-NMR) is a powerful experimental tool that allows to obtain information about the dynamic behavior of chemical compounds dispersed into a liquid environment. By using this technique, it is possible to elucidate the interactions between small species (ligands) and big structures (nanoparticle) in liquid state.

DOSY-NMR can be used as a diffusion-filtered 1 H-NMR experiment to eliminate the contribution of free and small molecules with fast diffusion (D = [10 -8 -10 -9 m 2 .s -1 ]) like impurities, free ligands or solvents, thereby leaving visible only the signals corresponding to larger species or Roberto González Gómez 85 systems with lower diffusion coefficients such as ligands interacting with the nanoparticle surface.

The DOSY NMR methodology has been already applied by several research groups in order to distinguish the signals corresponding to free ligands in solution from those of interacting ligands with the MNP surface. ([98], [START_REF] Guerrero | Efficient Ruthenium Nanocatalysts in Liquid -Liquid Biphasic Hydrogenation Catalysis : Towards a Supramolecular Control through a Sulfonated Diphosphine -Cyclodextrin Smart Combination[END_REF], [START_REF] Durand | DOSY technique applied to palladium nanoparticles in ionic liquids[END_REF])

Therefore, the DOSY-NMR technique was here used in order to determine the sample purity (presence or absence of free ligand), the hydrodynamic radius of the particles (metal core + ligand layer) and primarily about ethanoic acid interactions with the RuNPs surface. Thus, DOSY (1D and 2D) (L/G = 1.00). [START_REF] Farrar | Pulse and Fourier transform NMR: introduction to theory methods[END_REF] The higher-field peak provides clearly insights of the ethanoic acid coordination onto the RuNPs surface. Also, it shows how the chemical environment of the ligand change due to its interaction with the RuNPs, this phenomenon can be seen by the methyl protons chemical shift modification and corroborated by previous DFT studies.

Roberto González Gómez 86 The 2D-DOSY NMR experiment allows to distinguish different species by classifying them according to their mobility in the solvent and their hydrodynamic size. Signals of species which possess similar diffusion coefficient will probably belong to the same system or should have highly similar properties between them. [START_REF] Cohen | Diffusion NMR Spectroscopy in Supramolecular and Combinatorial Chemistry : An Old Paramete r -New Insights[END_REF] The 2D-DOSY NMR experiment for Ru x (CH The significant difference between these two diffusion coefficients confirmed the different interaction strength of the capping ligands at the NPs surface, namely a distension between weakly and strongly bonded ligands. The lower diffusion coefficient is attributed to the ligands in strong interaction with the metal surface (i.e. direct coordination) and the faster one is assigned to ligands with higher mobility that can be in fast exchange with free ligand in solution (outside the main coordination sphere).

The population of the strongly bonded species (45.0 %) must be considered as a minimal value. Indeed, a significant part of the broad signal weight corresponding to slow diffusion species Roberto González Gómez 88 detected at ca. 2.08 ppm lies outside the [2.2 -1.9 ppm] range, thus strongly bonded population is probably higher.

At this experimental stage of work, it was not possible to assure that all the ethanoic acid used for the RuNPs synthesis (0.4 equiv.) interacts with the metal system, because there exists the possible ligand removal in the cleaning process applied to the particles for their purification.

However, taking as a consideration that all the introduced ligand stays interacting as weakly or strongly bonded onto the RuNPs, it can be estimated from the TEM mean diameter, possible crystalline structure (hcp) and DOSY weighted signal averages (see section 6. Hydrodynamic radii were calculated using as a basis the diffusion coefficients observed and solvent viscosity (see section 6.1.3.7.1). The radii were found to be ca. 0.94 nm for the specie of lower diffusion coefficient and ca. 0.23 nm for the faster diffusing specie. From these results, the hydrodynamic diameters of the objects with the lowest coefficient diffusion can be estimated to be ca. 1.88 and 0.46 nm (radii x 2), respectively. It is important to remind that the hydrodynamic diameter includes both the metal core and the capping-ligand layer (scheme 2.5 a).

When comparing this value with the NPs mean diameter of ca. 1.5 nm obtained from TEM analysis, which represents only the metal core, a difference of ca. 0.4 nm is obtained. This difference corresponds to the organic layer thickness of the ethanoic acids surrounding the metal core. For comparison purpose, the hydrodynamic radius of the free ethanoic acid dimer was found to be ca. 0.4 nm. Consequently, the metal core calculated by DOSY can be adjusted to ca. 1.5 nm when eliminating the contribution of the organic layer, which is in very good agreement with that found by TEM studies. Concerning the calculated hydrodynamic diameter for the carboxylic species with higher diffusion coefficient (ca. 0.5 nm), this value is even bigger than that obtained for the free ethanoic acid dimer (ca. 0.4 nm). Therefore the presence of exchanging ligands interacting in a weaker mode with the metal surface and thus making them more dynamics in solution, can be proposed (scheme 2.5 b). ([44], [START_REF] Fan | Nanoparticle assembly of ordered multicomponent mesostructured metal oxides via a versatile solgel process[END_REF])

Roberto González Gómez 89 Liquid NMR techniques ( 1 H and DOSY) allowed to evidence the interaction and coordination of ethanoic moieties onto the RuNPs surface, and the experimental results were corroborated by a DFT-based analysis. Also, information about the ethanoic acid bonding nature, the formation of a hybrid material, the possible quantity of ligand attached directly at the NPs surface and the probable proton acid dissociation were obtained.

In the next section, theoretical studies as well as solid-state NMR and IR spectroscopies, will provide more information on the nature of the coordinated ligand.

Carboxylic Acid Possible Deprotonation

DFT chemical shift calculations previously described underline that the most probable structure, in agreement to the experimental NMR, found for the carboxylic moiety interacting with the nanoparticle surface is an ethanoate (carboxylate) coordinated in bridging mode (bidentate).

In order to answer this question, DFT-based thermodynamic and kinetic studies of the CH 3 COO-H bond dissociation were performed. Also, experimental solid-NMR and IR studies with their theoretical counterpart provided useful information that will be presented.

Roberto González Gómez 90

Carboxylic Adsorption Strengths and CH 3 COO-H Bond Dissociation

Previous published work had showed calculations regarding the formic acid proton dissociation (HCOO-H) on bare metal (0001) surface. They demonstrated that the process is an exothermic reaction in several transitional metals, for ruthenium it was observed that the value is of ca. 129 kcal.mol -1 . [START_REF] Herron | Trends in Formic Acid Decomposition on Model Transition Metal Surfaces : A Density Functional Theory study[END_REF] In another publication, it was reported some evidences of the proton acid bond dissociation in RuNPs stabilized by fullerenehexamalonic acid. [START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF] Both works point out that the carboxylic acids probably interact as carboxylates with RuNPs surface Two different models were built and optimized in order to consider the adducts adsorption energies, bond dissociation kinetics and final geometric properties. These models were built from a previously tested Ru 55 hcp NP initial model which is ca. 1.0 nm in size (see section 6.2.1). The theoretical findings were obtained by performing a series of periodic DFT calculations (see section 6.2.2). The mechanism and energy profile were obtained by calculating the adsorption energies of the different adducts in relation with the Ru 55 NP model (see section 6.2.3). The veracity of this methodology was reported in a previous publication. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] The first studied model (figure 2 The model 2 that was built as close as possible to the experimental findings provides reference data for an upper limit in terms of surface coverage, meanwhile, the model 1 represents the lowest limit with no surface species. The ethanoic acid ligand was adsorbed on the same site on the 1 and 2 models, i.e. edge between the (001) and (101) Ru 55 NP planes. The ethanoic acid adsorption energy on the bare Ru 55 NP is about -23.9 kcal.mol -1 (figure 2.25; 1 -CH 3 COOH*; black profile). When comparing with the adsorption energy of carbon monoxide (CO) on the same model (ca. -45.0 kcal.mol -1 ), ethanoic acid can be considered as a ligand moderately chemisorbed. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] This characteristic becomes less true for the model 2 due to a weaker adsorption energy of the ethanoic acid, -14.0 kcal.mol - ) [START_REF] Blanksby | Bond Dissociation Energies of Organic Molecules[END_REF] is overcompensated by the hydride adsorption and the formation of a five-membered dimetallacycle involving the ethanoate moiety and two ruthenium surface atoms.

Roberto González Gómez 93

Characteristic bond lengths are also given in figure 2.25, similar length trends were found for the naked (1) and crowded Ru 55 NP model (2). Ongoing from the adsorbed ethanoic acid to its ethanoate counterpart, the O-Ru bond length is reduced by ca. 0.06 Å, whereas both C-O bonds have the same length, only ca. 0.06 Å larger than a typical CH 3 C=O(OH) bond length, [START_REF] Leiserowitz | Molecular Packing Modes. Carboxylic Acids[END_REF] indicating the conjugation of the dimetallacycle.

Several calculations were performed in order to find the transitional state for the model 2 but it was not detected. This suggests a nearly barrierless CH The adsorption energy for each carboxylate-hydride species is -40.1 kcal.mol -1 (see section appendix A.4). This value is relatively close to the -29.9 kcal.mol -1 energy calculated for the dissociative adsorption energy on model 2 (figure 2.25; 2 -CH 3 COO*, H*). The addition of several ligands at the NP surface decreases the surface energy and the adsorption of a new moiety is less energetic, ([177], [START_REF] Liu | Ligand and ensemble effects in adsorption on alloy surfaces[END_REF]) thus highlighting the collective effect involved by the simultaneous adsorption of the ethanoic acids.

Solid-NMR Characterization

Heterogeneity, solubility and motion reduction (associated to dipolar couplings and chemical shift anisotropy) are some of the variables that can cause broad and weak signals in liquid NMR instead of sharp and well-defined ones. [START_REF] Hennel | Magic-Angle Spinning : a Historical Perspective[END_REF] In fact, this event is produced because of an increase on the T 2 relaxation time according to the next equation derived from the Heisenberg Uncertainty Principle. [START_REF] University | Relaxation in NMR Spectroscopy[END_REF] 𝑣 1/2 = 1 𝜋𝑇 2

By this way, the information obtained from solution NMR is not enough clear for determining the molecular structure or the intermolecular packing of ligands at the NP surface. [START_REF] Duer | Solid-State NMR Spectroscopy Principles and Applications[END_REF] In particular, this phenomenon is more evident for atoms close to the NP surface and even more importantly for those directly attached. Therefore, they cannot be identified by liquid-state NMR. [START_REF] Liu | Determination of monolayer-protected gold nanoparticle ligand-shell morphology using NMR[END_REF] The application of a high-speed rotation at the magic angle spinning (MAS) allows to reduce this phenomenon, thus leading to visible signals in solid-state NMR that are not accessible by solution NMR. Thus, information on ligand atoms in close proximity with the metal surface can be reached by solid-state NMR, making this technique a powerful tool to observe the ligand conformation in the metal nanoparticle periphery. For instance, [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C and 31 P solid-state NMR allowed to get precise data on the carbon and phosphorous atoms directly attached to the surface of RuNPs stabilized by carbenes [START_REF] Lara | Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity[END_REF] or phosphine ligands. [START_REF] Guerrero | Efficient Ruthenium Nanocatalysts in Liquid -Liquid Biphasic Hydrogenation Catalysis : Towards a Supramolecular Control through a Sulfonated Diphosphine -Cyclodextrin Smart Combination[END_REF] Owing these previous backgrounds, solid-state [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C CP Hahn-MAS NMR was performed on the Ru x (CH 3 COOH) 0.4 NPs in order to characterize more deeply their surface state. To avoid the formation of electric arcs between the NMR coils and rotor met with the purified RuNPs powder which was due to the high metal content, a THF colloidal suspension of the RuNPs sample was dispersed in mesoporous silica (see section 6.1.3.7).

Roberto González Gómez 95

The recorded spectrum is shown in figure 2.26. Two intense peaks are visible at ca. 24.2 and 66.8 ppm which are attributed to the carbon atoms from THF used to disperse the particles in silica. The shoulder observed in the foot of the THF signal at ca. 24.2 ppm, can be assigned to the methyl carbon of the carboxylic moiety molecular. The chemical shift of the carboxylic group in organic molecules is expected to be found in the region above 170.0 ppm. In the spectrum, the only signal visible over this zone is at ca. 186.0 ppm which is downfield shifted compared with the signal of the carboxylic carbon of the free ethanoic acid dimer found in solution NMR (THF-d 8 ;

171.7 ppm). [START_REF] Fulmer | NMR chemical shifts of trace impurities: Common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist[END_REF] The signal marked with an "x" is attributed to the THF degradation as well as the signals Taken as a base the same procedure as for 1 H-NMR, the assignation of the [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] As above mentioned, the carboxylic carbon signal corresponding to the free ethanoic acid dimer was found to be ca. 171.7 ppm in THF-d [START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] , but it can be shifted depending of the deuterated solvent used for the measurement; i.e. 175.8 ppm in benzene-d 6 , 176.0 ppm in chloroform-d and 177.2 ppm in D 2 O. [START_REF] Fulmer | NMR chemical shifts of trace impurities: Common laboratory solvents, organics, and gases in deuterated solvents relevant to the organometallic chemist[END_REF] The DFT calculated chemical shift for this specific carbon is 172 ppm (figure 2.27), a value which is in the range of the experimental shift reported and thus accurate enough to evaluate trends. This result points out that the DFT calculations have a good reliability. Since it was not possible to know any significant data form the methyl carbon, the carboxylic carbon was then evaluated. Hence, the carbon deshielded signal in comparison with free ethanoic acid dimer, can be assigned just to a direct coordination of the ligand onto the RuNPs surface. This data is supported by the broadness of the signal found in the experimental spectrum, the phenomenon is produced for the ligand reduced mobility and the metal surface heterogeneity.

In difference with the 1 H-NMR data which indicated the deprotonated species to be favored at the NP surface, the DFT [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-NMR chemical shifts cannot offer reliable conclusion about the carboxylic moiety molecular structure. It is not easy to distinguish between an ethanoate coordinated in a bringing mode and a σ-bonded coordinated ethanoic acid, because their chemical shifts overlap, [177 -186 ppm] and [180 -185 ppm], respectively (figure 2.30). Even it is not possible to rule out the presence of ligand in a π-coordination mode. However, the [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-DFTcalculations allow to discard the presence of free ligand.

Roberto González Gómez 99 It can be interfered from [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-NMR calculations and energy profile that ethanoate moiety is formed at the nanoparticle surface and stabilize the system with ethanoates interacting in a bidentate coordination mode. In the figure 2.31, it is summarizing the experimental and theoretical [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-NMR findings.

Roberto González Gómez 100

Vibrational Properties

Evidences of the free ligand absence and of the ethanoic moiety interaction with the RuNPs surface have been provided in previous sections. Also, insights in favor of the ethanoate coordination against the ethanoic acid have been shown by DFT chemical shift calculation ( 1 H and 13 C-NMR) and by CH 3 COO-H bond dissociation profile. However, till now there is no experimental evidence that supports this finding. Thus, to complete this study and answer the question of the molecular structure of the ligand attached onto the metal surface, an FTIR analysis on a solid sample of purified Ru x (CH 3 COOH) 0.4 NPs was performed in the ATR mode, using a spectrophotometer installed inside a glove box (see section 6.1.3.3). The obtained spectrum was first compared with the experimental fundamental peaks of sodium ethanoate in liquid [START_REF] Jones | Infrared Spectra of CH3COONa and CD3COONa and Assignments of Vibrational Frequencies[END_REF] and solid state ([184], [START_REF] Noma | Infrared and Raman intensity parameters of sodium acetate and their intensity distributions[END_REF]) (figure 2.32).

Roberto González Gómez 101 The experimental FTIR spectrum shows a small broad vibration band at ca. 3400 cm -1 attributed to the symmetric (ν s ) and asymmetric (ν as ) stretching vibration modes of water. The presence of this molecule was previously noticed in the 1 H-NMR spectrum but even after long period under high-vacuum it was not possible to totally remove it.

The bands observed at ca. 2970 cm -1 are attributed to the ν as and ν ss vibration modes of the methyl group of the carboxylic moiety ((CH 3 )COO(H)). No carboxylic acid (R(C=O)OH) stretching vibration bands are visible in the region [1850 -1600 cm -1 ], indicating the absence of free or coordinated ethanoic acid for which a vibration band is expected at ca. 1800 cm -1 in standard conditions. [START_REF] Wilmshurst | Infrared Investigation of Acetic Acid and Acetic Acid-d Vapors and a Vibrational Assignment for the Monomeric Acids[END_REF] Instead, a band at ca. 1545 cm -1 can be found and it is attributed to the ν as vibration mode of a carboxylate (CH 3 (C=O)O) thanks to its similarities with the sodium ethanoate spectrum. [START_REF] Jones | Infrared Spectra of CH3COONa and CD3COONa and Assignments of Vibrational Frequencies[END_REF] At lower energies, two well separated bands between 1500 and 1300 cm -1 can be observed.

Compared to the sodium ethanoate spectrum, they can be attributed to three different vibration modes, the asymmetric stretching mode ν as of the carboxylate group (CH Meanwhile, the ν as vibration mode of the ethanoate (CH 3 (C=OO)) is slightly underestimated and Roberto González Gómez 103 they are found between [1500 -1300 cm -1 ], this effect can be attributed to the overestimation of the Ru to COO back-donation. [START_REF] Zhong | Probing the electronic and catalytic properties of a bimetallic surface with 3 nm resolution[END_REF] The last five bands are in a good agreement with the normal modes of vibration calculated for this model.

Due to the different coordination modes of the hydrides that lie on the studied theoretical model, the Ru-H harmonic frequencies (figure 2.33 blue) can be found in a high range of frequencies from [1600 to 400 cm -1 ]. Except one mode of vibration that corresponds to the hydride η coordination mode that appears around 1950 cm -1 , which could be assigned to a small peak observed in the experimental spectrum at the same frequency range. was found in in 2 -CH3COOH* model at 1680 cm -1 . Since no band were observed around 1700 cm - 1 in the experimental spectrum, the hypothesis of the presence of a mixture of entities as in the 2 -CH3COOH* model cannot be supported.

But as silicon grease and perfluoropolyeter (PFPE) lubricant were used to maintain inert atmosphere during the Ru x (CH 3 COOH) 0.4 NPs synthesis, band a can be assigned to the PFPE presence, [START_REF] Cui | Infrared Spectrum Analysis of Perfluoro Polyethers (PFPE) of Fluorocarbon-based Magnetic Fluid's Base Liquid[END_REF] meanwhile c and d signals are attributed to those of silicon grease. [START_REF] Mayo | Course notes on the interpretation of infrared and Raman spectra[END_REF] The presence of these pollutants was also observed in the 1 H-NMR spectrum.

To finish, THF could be responsible for the peak b and the weak peak close to 1950 cm -1 , that were previously noted to possibly correspond to Ru-H η vibration mode, due to its presence during the RuNPs purification process (see section 2.5.3). Also, the THF under certain catalytic conditions can be polymerized (PTHF) which has a vibration mode at ca. 1110 cm -1 . [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] Thus the band b could be assigned to PTHF. Previous published study has proved the THF decarbonylation Roberto González Gómez 104 in the presence of RuNPs leading to the presence of a carbonyl vibration on FTIR spectra. [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF] Thus, the small peak here found at ca. 1950 cm -1 can be also assigned to the presence of CO.

As a conclusion of this section, the normal modes analysis together with the sodium ethanoate data provide a clear assignment of most of the experimental FTIR bands observed for Ru x (CH 3 COOH) 0.4 NPs. These results combined with the experimental and theoretical 1 H and 13 C-NMR and the CH 3 COO-H bond dissociation profile point out that all the ligands surrounding the RuNPs are not under the carboxylic acid form but deprotonated as ethanoates.

Surface Composition

The nanomaterials surface composition has an important influence on their size, solubility and surface state of these metal systems. ([191], [START_REF] Canzi | Diffusion-Ordered NMR Spectroscopy as a Reliable Alternative to TEM for Determining the Size of Gold Nanoparticles in Organic Solutions[END_REF]) The catalytic performance of such systems depend on the surface energy of the nanoparticle, due to adsorption-desorption processes and to the influence of stabilizing ligands on surface energy. ([177], [START_REF] Lu | Magnetic nanoparticles: synthesis, protection, functionalization, and application[END_REF]) A catalyst will have the best performance when this ratio is fully optimized. [START_REF] Zhang | Bimetallic Nanostructures: Shape-Controlled Synthesis for Catalysis[END_REF] Apart from elucidation of ligand coordination mode at NP surface, the knowledge of the ligands present at the surface and of the surface coverage is an important prerequisite in order to shed light on the possible relationship between these properties and the catalytic activity of such materials. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] Therefore the surface composition becomes a crucial parameter to be studied.

Experimental Titration of Surface Hydrides

The synthesis of Ru x (CH 3 COOH) 0.4 NPs has been performed by the decomposition of a ruthenium metal precursor in the presence of reductive atmosphere (H 2 ). The presence of hydrides at the NPs surface has been demonstrated as a consequence of the synthetic conditions in different metals, ([195], [START_REF] Cano | Enantioselective hydrogenation of ketones by iridium nanoparticles ligated with chiral secondary phosphine oxides[END_REF]) including ruthenium. [START_REF] Philippot | Organometallic Ruthenium Nanoparticles and Catalysis[END_REF] It has also been seen than these hydrides seem to be highly reactive. [START_REF] Philippot | Organometallic Ruthenium Nanoparticles and Catalysis[END_REF] CHAPTER II The reductive formation of norbornane was measured by GC. Indirectly, the reaction yield allows the determination of reactive hydrides that are responsible for the 2-norbornene reduction.

Furthermore, this data permits to calculate the hydrides surface coverage on the Ru x (CH 3 COOH) 0.4

NPs by considering the nanoparticles mean size obtained by TEM microscopy (ca. 1.5 nm) and the estimated crystalline structure observed by HRTEM (hcp).

The calculated value was ca. 0.3 reactive hydrides per ruthenium surface atom (0.3 H reac /Ru surf ). This value means that at room temperature there are at least 25 hydrides per ruthenium nanoparticle (25 H/Ru NP ) for these Ru x (CH 3 COOH) 0.4 NPs.

The hydrides titration for these nanosystems appears a bit low compared to values previously reported for other ligand-stabilized RuNPs that were in the range [1.0 -1.6

H reac /Ru surf ]. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] This result thus shows an important difference in terms of metal surface state of the nanoparticles with less surface hydrides present. Therefore, their evaluation in catalysis is an important goal to be achieved.

Roberto González Gómez 106

DFT Titration of Surface Species

In this section, it will be shown that it is possible as well to theoretically evaluate the number of ethanoates and hydrides at the surface of the Ru x (CH 3 COOH) 0.4 NPs. As a reminder, the experimental titration of reactive hydrogen atoms at r.t. by an indirect olefin reductive reaction has been shown in the section 2.5.1. However, due to experimental issues a reliable titration of the ethanoates at the Ru NPs surface was not fully accomplished (see section 2.3.2). Thus, the DFT titration of surface species can be a complementary and powerful tool to map the surface state of the Ru x (CH 3 COOH) 0.4 NPs an get information about the quantity of capping-ligands and determine a precise surface composition of the RuNPs.

It is indeed possible to calculate the Gibbs free energy and other thermodynamic functions of solids and liquids, using first principles methods. Such approach, the so-called ab initio thermodynamics method, has successfully been applied to explain or predict thermodynamic material properties, and in particular surface properties. ([197]- [START_REF] Reuter | ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions[END_REF])

The DFT energies obtained from optimized structures covered by organic molecules are calculated without taking into consideration the concentrations, pressure or temperature variables which are crucial in the systems behavior and on surface coverage. Yet, adding the zeropoint energy correction to a DFT energy only leads to the 0 K internal energy. This ab initio thermodynamics methodology allows to extend the applicability of DFT to realistic environmental conditions in terms of temperature, pressure and composition of the gas and liquid surrounding phase, which is considered as a reservoir of species in equilibrium with the metal NPs.

The procedure has recently been applied to ruthenium surfaces and NPs with a good agreement to experimental findings, those studies were enforced to ruthenium systems in equilibrium with molecular hydrogen only or with syngas (H 2 & CO). ([82], [START_REF] Rosal | A density functional theory study of spectroscopic and thermodynamic properties of surfacic hydrides on Ru (0001) model surface: The influence of the coordination modes and the coverage[END_REF]- [START_REF] Cusinato | Shape, electronic structure and steric effects of organometallic nanocatalysts: relevant tools to improve the synergy between theory and experiment[END_REF])

The robustness and predictability of this approach was thus here evaluated for the Ru x (CH 3 COOH) 0. Is hidden in ∆𝐺 ° and in the chemical potentials 𝜇(𝐿 1 ) and 𝜇(𝐿 2 ), (see section 6.2.6).

The studied systems possess a large number of atoms and electrons, the planewave basis set is large (or to be more explicit, the cutoff value is large) and owing to their diameter, the unit cell must be large enough to avoid spurious interactions between images. Therefore, a direct optimization of the built structures is computationally highly demanding. Thus, a progressive optimization of the ligand coverage ratio was performed in order to save computational resources Roberto González Gómez 109

(
Gibbs free energies, Δ a G° (T, 𝑝 𝐻 2 , C acid ) were calculated for each one of the 44 structures at three different temperatures (T = 200, 300 and 450 K) by taking into account the DFT energy of the optimized systems and the ligand-metal vibration corrections (see section 6.2.7 and appendix D). ([199]- [START_REF] Cusinato | Shape, electronic structure and steric effects of organometallic nanocatalysts: relevant tools to improve the synergy between theory and experiment[END_REF]) Even though the acid-metal and ethanoate vibrations have been taken into account, it must be underlined that the Ru-H vibrational contribution to Δ a G° is the highest (for a comparison of 1D phase diagrams with and without vibrational contributions. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] The thermodynamic model used for the Gibbs free energy calculations and hence the chemical potentials consider H 2 as an ideal gas and the acid as an infinitely dilute solute in the presence of THF. ).

From the 44 calculated structures only In order to make a link with the actual experimental conditions, the ethanoic acid needs to be considered that the quantification was performed at room temperature and that experiment quantify active hydrides. Thus, as a conclusion this theoretical investigation confirms that ab initio thermodynamics accurately account for the number of hydrides coordinated at the nanoparticle surface and it confirms the lower number of adsorbed hydrides in this nanosystem, compared to usually observed and calculated amounts in other RuNPs. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] In the other hand regarding ethanoates, DOSY-NMR studies showed the existence of two types of ligands, strongly (ca. 45.0 %) and weakly bonded (ca. 55.0 %). In order to be compared with the theoretical model, only the ethanoates which have a strong interaction with the metal surface are here studied. Thus, it can be inferred that approximately 28 ).

In this case, 8 Ru 55 NP among the 44 calculated structures also are found to be the more The decrease in temperature (ΔT = -100 K) involves a lowering of the adsorption Gibbs free energy of the ligands (Δ a G°) and an increase of the surface energy of the nanoparticles. [START_REF] Lopez | On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation[END_REF] As a result the surface coverage of the metal nanoparticle is increased that is why optimized structures covered by only hydrogen cannot be found. Also, it explains the appearance of domains with higher quantity of organic molecules i.e. domain 41 & 35, their coordinates can be seen in section appendix F. In other words, the lower the temperature the higher the quantity of ligands that can be present at the Ru 55 NP surface, as expected. In this case the carboxylate form is preferred due to its higher adsorption energy in comparison with that of the hydrides (see section appendix A).

The hypothetic experimental conditions are slightly affected by the temperature, thus a similar equilibrium pressure and concentrations as those found at r.t., i.e. an hydrogen pressure of [10 -5 -10 -2 bar] and an ethanoic acid concentration in the range [10 -4 -10 ).

Previously published studies have demonstrated that the The temperature increase involves to significantly decreasing higher the temperature the lower the catalytic activity in some nanosystems, due to the increase in the system mobility. Also, it has been seen that the adsorption energy of the binding ligand increases letting to a decrease of the surface coverage. [START_REF] Arnal | High-temperature-stable catalysts by hollow sphere encapsulation[END_REF] As it can be seen in the phase diagram calculated at 450 K (figure 2

On the Possible Presence of THF at the NPs Surface

In this study, the Ru x (CH 3 COOH) 0.4 NPs were washed with THF prior to spectroscopic studies and used as deuterated solvent for liquid and solid NMR experiments. This opens the possibility for some THF molecules to be adsorbed on RuNPs. Yet, in a previously published work, the presence of THF at the RuNPs surface has been indirectly observed due to its possible polymerization. [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] As well, due to its decomposition via a decarbonylation [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF] .

It is also known that the THF, which is a polar aprotic solvent, has the ability of assist in the MNPs stabilization by coordinating at the NPs surface in some metals (Pt and PdNPs) ([205], [START_REF] Rodriguez | Synthesis and Isolation of Cuboctahedral and Icosahedral Platinum Nanoparticles[END_REF]) but for RuNPs it has been described as simple synthesis assistant or as pollutant mostly after its reaction ar the NP surface. [START_REF] Pan | A New Synthetic Method toward Bimetallic Ruthenium Platinum Nanoparticles[END_REF] Till now, there is not a clear proof of the RuNPs formation by using just THF as stabilizing agent. [START_REF] Vidoni | Novel, Spongelike Ruthenium Particles of Controllable Size Stabilized Only by Organic Solvents[END_REF] Experimental characterization of Ru x (CH 3 COOH) 0.4 NPs provided evidences of the THF presence onto these RuNPs. Signals present in FTIR and solid-state NMR experiments have been attributed as coming from THF. In order to evaluate the possible presence of THF, a first evaluation of its ligand viability and stabilizing strength was performed.

A RuNPs synthesis with higher inert conditions and lower presence of oxidants was achieved by using THF both as solvent and stabilizing agent (Ru x (THF) y ). After evacuation of remaining hydrogen (H 2 ), a semi-stable suspension was obtained which was concentrated under high-vacuum before preparation of a grid in order to perform TEM analysis. The micrographs show the presence of two different types of particles: Big metal agglomerates of ca. 40.0 nm and heterogeneous RuNPs with a mean size of ca. 2.9 ± 1.8 nm (figure 2.41), which is a mean size close to that obtained for RuNPs stabilized with alcohols, such as propanol or heptanol. [START_REF] Pelzer | Organometallic Synthesis of Size-Controlled Polycrystalline Ruthenium Nanoparticles in the Presence of Alcohols[END_REF] Roberto González Gómez 119

These finding proves the ability of this solvent to be used as a stabilizer. The formation of agglomerates beside quite large and heterogeneous RuNPs also indicates that it is not the best stabilizing agent, despite the high quantity of THF present in the reaction media. These findings point out that THF can be adsorbed at the RuNPs surface. However, it behaves as a poor electron donor ligand, thus it is unable to reduce the ruthenium nanostructure surface energy, which leads to a poor control of the nanoparticle size and the formation of agglomerates. ([93], [START_REF] Kim | Size-selective synthesis of gold and platinum nanoparticles using novel thiol-functionalized ionic liquids[END_REF])

Despite these results, the presence of THF on preformed Ru x (CH the possible competition that could happen between THF and the carboxylic species on the metal surface. The selected hydrogenated model was used with the aim was to decrease the nanoparticle reactivity by partially saturating the NPs surface to offer more relevant results. [START_REF] Nilekar | Preferential CO oxidation in hydrogen: reactivity of core-shell nanoparticles[END_REF] The THF adsorption strength is not very sensitive to the hydrogen surface coverage, with adsorption energies that lie between ca. [-16.2 --21.2 kcal.mol -1 ] (see section appendix C.2). Given its low adsorption energy, THF can be considered as moderately chemisorbed. Its adsorption strength is similar to the dissociative adsorption energy of H 2 at the same level of calculation (ca. -11 kcal.mol -1 x 2; see appendix A.1), which suggests that it can dynamically interact at the surface, as hydrogen does, provided that the adsorption barrier height is low.

When compared the THF adsorption energy with that of the ethanoic acid ca. [-17.8 --25.8 kcal.mol -1 ], it appears to be slightly weaker but not significantly enough (see section appendix C.1)

to rule out a possible exchange between these two molecules. At certain point the energies can be similar which led them to a surface area competition or in a ceaseless exchange (scheme 2.9).

Roberto González Gómez 120

Scheme 2.9 Representation of the possible continuous ligand exchange between ethanoic acid or hydrogen and THF.

Previously it was proven, both experimentally and theoretically, that ethanoic acids are deprotonated. Their dissociative adsorption energies are stronger via values in the range [-40.1 --51.1 kcal.mol -1 ] (see section appendix A.3.2). Therefore, it is suggested that THF can hardly compete with ethanoates onto the Ru 55 NP. Also, it explains why controlled and small RuNPs can be synthetized by using ethanoic acid and particles are they are not well-formed when THF is used as stabilizing agent. These results support the relevance of the ligand donor strength in the RuNPs formation.

Since the nanoparticles are covered by ethanoates and not ethanoic acid, at this point becomes difficult to support the hypothesis of having THF coordinated at the RuNPs surface. It is worthy to point that the THF came in contact with the nanoparticles while being already formed (for purification and solution NMR experiments). Thus, in order to have more reliable data it is necessary to evaluate the possible THF presence on ligand-crowded Ru 55 NP.

To achieve this goal, the THF adsorption energy onto RuNP surface was tested and compared on the model 2 used previously to evaluate the CH 3 COO-H bond dissociation (see section 2.4.1). This model has a crowded surface and was demonstrated to have a ligand surface coverage ratio (Ru(CH 3 COO) 15 (H) 32 ) similar to the optimal compositions found in the phase diagram at 300 K (see section 2.5.2).

CHAPTER II Surface Composition

Roberto González Gómez 121

The grafting of THF on the model 2 metal surface, which involves the σ-donation of one oxygen lone pair to a ruthenium atom, is stable by -28.6 kcal.mol -1 (figure 2.42) offering a plausible data of the THF presence when comparing the same adsorption procedure with the ethanoic acid (-14.0 kcal.mol -1 ) model 2 CH 3 COOH* or ethanoate (-29.9 kcal.mol -1 ) model 2 CH 3 COO*, H*. This result suggests the possible presence of a very few number of THF molecules at the nanoparticle surface, not because of a ligand exchange with ethanoates, but rather with hydrides.

Nevertheless, this result needs to be taken with caution because none steric hindrance effect from the ethanoates was considered. ).

According to the experimental synthetic conditions, three hypothetical stable surface Roberto González Gómez 124

Electronic Properties

Knowledge on the electronic structure of the nanoparticles is essential in order to understand their reactivity. In fact, a suitable catalyst for a given reaction has to present an optimal interaction (adsorption/desorption) between the reactants and the chosen catalyst (adsorption energy). [START_REF] Sabatier | How I Have Been Led to the Direct Hydrogenation Method by Metallic Catalysts[END_REF] The catalyst-reactant interactions will depend on the electronic properties of the particles and thus can vary following the NP general structure or the ligand coverage ratio. Also, it is possible to establish a relationship between the activation energy in a given reaction and the adsorption energy of the reactant molecules onto the NP surface. This phenomenon can be studied using the BrØnsted-Evans-Polanyi relation ([211], [START_REF] Evans | Inertia and driving force of chemical reactions[END_REF]) or the volcano plots. [START_REF] Balandin | Modern State of the Multiplet Theory of Heterogeneous Catalysis[END_REF] Therefore, it is important to know the electronic properties of the Ru x (CH 3 COOH) 0.4 NPs in order to evaluate its utility as a catalyst. These studies will be described in the following sections.

Roberto González Gómez 125

Electronic States

In order to describe the electronic properties of metal clusters and MNPs, a different approach is required, given the complexity of these systems. ([214], [START_REF] Gruner | Multiply twinned morphologies of FePt and CoPt nanoparticles[END_REF]) The density of states (DOS) is a special characteristic of these nanomaterials, which represents the interacting molecular orbitals in MNPs. In other words, this approach allows to determine the occupancy of these states, and thus their electronic properties. [START_REF] Wehling | Molecular doping of graphene[END_REF] The electronic structure of the Ru 55 covered NP was evaluated with the Lobster software, where the projector augmented waves (PAW) of the electronic states were projected on a local Slater atomic basis set, hence giving the possibility to derive several properties and indexes, such as projected density of states (pDOS), crystal orbital hamilton population (pCOHP) and bond strength indexes (IpCOHP) see definitions and methodology in section 6.2.9 & 6.2.10, respectively.

For this study a Ru 55 NP model which has similar ligand coverage as the optimal one found in the phase diagram at 300 K was used. The density of states determination and orbital-like analysis were realized for the 2 CH 3 COO*, H* model by following a published procedure. ([82], [START_REF] Del Rosal | Ligand-Field Theory-Based Analysis of the Adsorption Properties of Ruthenium Nanoparticles[END_REF])

The interaction between electrons occupying d-type orbitals of the metal nanoparticle and those of the adsorbate can be correlated to the adsorbate-substrate adsorption energy. [START_REF] Gorzkowski | Probing the Limits of d-Band Center Theory: Electronic and Electrocatalytic Properties of Pd-Shell-Pt-Core Nanoparticles[END_REF] The representation of these NP electrons is so-called d-band center. ([219], [START_REF] Hammer | Electronic factors determining the reactivity of metal surfaces[END_REF]) Thus, the electronic Roberto González Gómez 126 The d-band center is a well-known parameter to determine the reactivity of these types of systems and there is a correlation with the surface coverage and adsorption strength of the adsorbates. For example, the d-band center value reported for a Ru 55 NP covered with a similar amount of hydrides (35) but no ethanoates lies at -2.82 eV, [START_REF] Cusinato | Chimie de Surface de Nanoparticules de Ruthenium: Approches Théoriques[END_REF] which evidences that a Ru 55 NP is more reactive in the absence of ethanoates (higher d-band center value). This can be related to the adsorption strength of the hydrides vs ethanoates at the same level of theory (ca. -14.2 vs -40.1 kcal.mol -1 ).

The grafting of ethanoates on the metal surface also involves a weakening of the Ru-Ru It has been reported previously that the highest occupied states are essentially developed upon metal atoms, and that they exhibit an anti-bonding character. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] In the plotted -pCOHP Roberto González Gómez 127

(figure 2.45) this phenomenon can be observed. Also, it is worth mentioning that some electrons populate anti-bonding C-O states (figure 2.45 blue) that lie at the same energy as bonding Ru-C states (figure 2.45 red). This event can be analyzed as a weak back-donation from the metal surface to the π* MOs of the carboxylate groups. The phenomenon can be correlated with the increasing of the average C-O bond length calculated in section 2.4.1.

Atomic Charges in RuNP

Both experimental and theoretical characterization data point out to the presence of ethanoate at the surface of the RuNPs rather than of ethanoic acid. Given that ethanoate is not electrically neutral, but possesses a delocalized negative charge, the knowledge of the evolution of atomic charges in the RuNPs upon its coordination is of high interest.

In order to know evaluate the influence of grafted carboxylates on the possible oxidationof the surface ruthenium atoms oxidation. Bader charges ([221], [START_REF] Group | Bader Charge Analysis[END_REF]) as well as the Mulliken population analysis (pMPA charges) obtained by integrating the pDOS were calculated (see section 6.2.9).

These methods have been previously reported for describing the surface state of MNPs, ([223], [START_REF] Okumura | Theoretical investigation of the hetero-junction effect in PVP-stabilized Au13 clusters. The role of PVP in their catalytic activities[END_REF]) but since they are based in different level of theory their reliability needed to be first evaluated for this nanosystem.

The 2 CH 3 COO*, H* model was evaluated by these methods due to its closeness to the optimal ligand surface coverage found for Ru 55 NP at 300 K. The average atomic charge of the hydrides calculated by the two methods (Bader vs. pMPA: q H = -0.19e/-0.20e) do not show any significance difference. Also, the global charges hold by the ethanoates (Bader vs. pMPA: 𝑞 𝐶𝐻 3 = 0.14e/0.07e; 𝑞 𝐶𝑂𝑂 = -0.67e/-0.55e) as well as the overall charge of the Ru 55 NP (Bader vs. pMPA:

𝑞 𝑅𝑢 = 0.27e/0.26e) are found to be similar with both methods.

The main differences lie in the atomic charges of the individual elements that form the ethanoate (Bader vs. pMPA: 𝑞 𝐶 𝐶𝑂𝑂 = 1.52e/0.64e; 𝑞 𝑂 = -1.10e/-0.59e; 𝑞 𝐻 𝐶𝐻 3 = 0.07e/0.33e; 𝑞 𝐶 𝐶𝐻 3 = -0.07e/-0.91e) as well as in the average charge hold by the 11 core metal atoms (Bader vs. pMPA:

𝑞 𝑅𝑢 𝐶 = 0.04e/-0.12e). Whereas the two methods agree in concluding that surface Ru atoms are significantly oxidized (Bader vs. pMPA: 𝑞 𝑅𝑢 𝑆 = 0.33e/0.35e), they differ about the charges of the Roberto González Gómez 128 core atoms. According to the Bader analysis they are almost neutral whereas they are slightly negatively charged according to pMPA. In summary, the most striking difference between Bader and pMPA charges is observed for the core metal atoms and for the individual elements of the ethanoates.

Even when there is not a reinforced experimental data where the chosen methodology can be supported, the pMPA charges are consistent with the pCOHP obtained data and d-band

center. Also, a recent published work reported that the pMPA charges are very similar to Natural Population Analysis charges [START_REF] Reed | Natural population analysis[END_REF] in doped graphene. [START_REF] Gerber | Critical assessment of charge transfer estimates in non-covalent graphene doping[END_REF] Therefore the Mulliken population analysis will be preferred to analyze this system. It is also worth mentioning that according to the charge calculations, all adsorbed hydrogen atoms in ethanoate-capped ruthenium NPs have an hydridic character, even those that originate from the acids.

Previous published work exhibits that for the same Ru 55 NP system but grafted by carbon monoxide (Ru 55 (CO) 66 ), the ruthenium surface atoms are less oxidized (𝑞 𝑅𝑢 𝑠 : 0.25e). [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] The result is not in contradiction with a low π-acceptor character of CO when coordinated to Ru surfaces and it underlines the ability of ethanoate and hydrides to deplete the electronic density of surface Ru atoms. It is also worth mentioning that according to the charge calculations, all adsorbed hydrogen atoms in ethanoate-capped Ru 55 NPs (𝑞 𝐻𝑦𝑑𝑟𝑖𝑑𝑒 : -0.20e) have an hydridic character, even those that originate from the carboxylic acid deprotonation.

Hydrogen Evolution Reaction: A Possible Application

RuNPs are well-known as interesting materials for hydrogenation catalytic reactions. ([59], [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF])

and more recently it have been observed their potential catalytic activity towards the hydrogen evolution reaction (HER). [START_REF] Drouet | A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions[END_REF] In this work, it has been introduced the use of small alkyl chain length carboxylates as new coating species on RuNPs. For its relevance and previous background, it is worthy to test this nanosystems Ru x (CH 3 COOH) 0.4 for HER applications in the electrolysis of water. Due to the good correlation between the experimental and the computational chemistry characterization, this issue can be evaluated firstly form a theoretical point of view.

According to the seminal work of NØrskov, there is a correlation between the H 2 dissociative adsorption Gibbs free energy and the exchange current for hydrogen evolution reaction (HER). [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] Roberto González Gómez 130

∆𝐺 𝐻 * = 1 𝑛 [𝐺(𝐻 * ) -𝐺(𝑠𝑢𝑟𝑓) - 𝑛 2 𝐺(𝐻 2 )]
A Balandin-Sabatier volcano curve had been found, with platinum electrodes on top of the volcano and ΔG H* that lies between -2.0 and 0.7 kcal.mol -1 as a function of H coverage. The main conclusion of this study is that the requirement for an optimal HER catalyst is that the Gibbs dissociative adsorption energy of H 2 must lie as close as possible to 0 kcal.mol -1 .

As it was shown in this published work in addition to several experimental findings, Pt-based catalysts show a high efficiency for reducing protons to H 2 in acidic media (H 3 O + ).

However, there is a need to find alternative HER catalysts in order to improve their capability and reduce the production costs. Ruthenium, even though is not an abundant metal, can be considered as an interesting candidate to test as catalyst in the HER reaction, due to its closeness to fulfill the H adsorption energy criterion (ΔG* ca. [-6.4 to -5.6 kcal.mol -1 ] for [0.25 -1.00] hcp monolayer (ML) on Ru (0001)) [START_REF] Rosal | A density functional theory study of spectroscopic and thermodynamic properties of surfacic hydrides on Ru (0001) model surface: The influence of the coordination modes and the coverage[END_REF] after the empirical addition of 5.5 kcal.mol -1 , as representative thermal energy for transitional metals. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] ∆𝐺 𝐻 * = ∆𝐸 𝐻 + ∆𝐸 𝑍𝑃𝐸 -𝑇∆𝑆 𝐻 ∆𝐺 𝐻 * = ∆𝐸 𝐻 + 0.24 𝑒𝑉

As was previously mentioned in section 2.6.1, there is a high compromise between the adsorbate-substrate adsorption energy and the catalytic performance. [START_REF] Gorzkowski | Probing the Limits of d-Band Center Theory: Electronic and Electrocatalytic Properties of Pd-Shell-Pt-Core Nanoparticles[END_REF] Thus, due to the weak adsorption of the hydrogen onto Ru 55 NP (ca. [-12.0 --14.0 kcal.mol -1 ]), it could led to a decrease of this catalytic cooperative effect and even more when the co-adsorbed ligands have a strong affinity to the metal surface.

The previous planted phenomenon could be observed in a previous published work, where the RuNPs were exposed to syngas showing that all the grafting free Ru sites were occupied by carbon monoxide and no for hydrides. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] On the contrary, for this ethanoic acid-capped RuNPs, it was both experimentally and theoretically possible to found hydrides co-adsorbed with ethanoates (Exp: 0.3 H reac /Ru surf ; Theo: [0.4 -0.6 H/Ru surf ]) at 300 K (r.t.). The fact that ethanoic acid-capped RuNPs can accommodate both ligands at their surface makes them potentially interesting candidates for HER.

Roberto González Gómez 131

The adsorption energy of hydrogen (ΔE H ) has been calculated (see section 6. This can be interpreted in terms of ΔG H* by applying the thermal energy previously described. It can be seen that these values oscillate from [-6.8 to -10.3 kcal.mol -1 ] for the selected Ru 55 NP Roberto González Gómez 132 adsorption sites. These values are high enough to make the adduct desorption a difficult and energetic process, and consequently not favorable which indicates that this Ru 55 NP model is probably a non-suitable catalyst for HER, as expected.

Given these first results, it appears that a more suitable for the HER reaction will require a lower hydrogen adsorption energy than the Ru 55 NP, but still strong enough for the hydrogen to coordinate to the metal atoms. This phenomenon can be induced by reducing the surface energy of the NP system. Therefore a hydrogen crowded stable structure Ru 55 (CH 3 COO)(H) 54 found in the phase diagram at 450 K was evaluated (figure 2.47 b).

In this model the presence of hydrides coverage lowered significantly the atomic d-band center of the Ru atoms, which can be correlated with a decrease in the ΔG H* (+2.0 --8.6 kcal.mol -1 )

with regards to Ru 55 naked NP.

As it was seen saturated hydrogen NP seems to be more suitable catalyst for the HER reaction having some sites of high interest (plane ( 101)), but the Gibbs free energy calculated for the five different sites appears to be highly affected for the NP site and its chemical environment.

Even so with this composition it is found a better catalyst but no really promising for be tested for this catalytic reaction.

The last saturated Ru 55 NP model evaluated possess less quantity of hydrides but higher amount of strongly adsorbed ethanoate ligands, Ru 55 (CH 3 COO) 16 (H) 16 . This model was shown to be one of the two stable structural domains found in the phase diagram at 300 K, and having a ligand coverage ratio quite similar to that found in the experimental characterization. published for HER reaction. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] All together, these theoretical results show the ethanoic acidstabilized RuNPs to be a promising nanocatalyst for the HER reaction.

Conclusion

This chapter provided extended theoretical and experimental characterization studies on RuNPs stabilized by ethanoic acid (CH 3 COOH). Hence, this conclusion arises in order to summarize the whole study of the principal analyzed system Ru x (CH 3 COOH) 0.4 .

The synthesis of these particles has been performed in mild conditions following the organometallic approach, by decomposing a pentane solution of the ruthenium precursor, Ru(COD)(COT), under 3 bar H 2 at r.t. The novelty of this work is the use of a carboxylic acids as a stabilizer while there is only one example reported in the literature, with a C60-based carboxylic acid (C 66 (COOH) 12 ). What is also relevant is the fact that ethanoic acid bears a very short alkyl chain, meaning that it cannot be expected to have an influence of the alkyl group on the stabilization of the RuNPs as often observed with stabilizers having alkyl groups with long chain length. Also, it is important to mention the relevance of the solvent used, pentane, which is not known as contribute to the stabilization of metal nanoparticles as THF can do for instance. By this way, the use of ethanoic acid and pentane was a synthesis challenge.

Roberto González Gómez 134

But this strategy appeared to be efficient and an optimized system of RuNPs was obtained with a [ligand]/[Ru] molar ratio of 0.4 equiv. leading to Ru x (CH 3 COOH) 0.4 sample. As evidenced by TEM and WAXS analysis, the obtained RuNPs display a small size centered at ca. 1.5 nm and a poorly crystalline structure with a few plans attributed to the hcp crystalline structure of bulk ruthenium. Indeed, the nanosystem was not perfectly controlled in terms of shape and crystalline structure. However, this nanomaterial was a very interesting case study in order to get accurate and relevant data on the surface properties of these RuNPs by two complementary approaches, namely experimental and theoretical chemistry.

Strong efforts have been performed in order to characterize as precisely as possible the surface composition of these nanoparticles and also to evaluate their surface reactivity. For this purpose, both state-of-the-art techniques in nanochemistry including spectroscopic techniques such as IR and solution and solid-state NMR, and theoretical chemistry tools have been used in parallel.

This combination of tools appeared to be very powerful to get qualitative but also quantitative information on the surface state of the particles. All together the obtained results converged towards the coordination of the ligand at the ruthenium surface under ethanoate form, preferably in a bidentate mode. This result is in agreement with a small activation barrier of CH 3 COO-H bond dissociation.

Moreover, the results evidenced that the coordination of the ethanoate at the ruthenium surface does not restrain the co-adsorption of a significant amount of hydrogen atoms, making the surface composition of the RuNPs to be a mixture of ethanoates and hydrides.

The DFT titration showed an optimal surface composition of ca. [0.4 -0.6] H/Ru surf and 0.4 CH 3 COO/Ru surf at 300 K. These data are in high accordance with the experimental quantification ones, namely ca. 0.3 H reac /Ru surf and 0.3 CH 3 COO/Ru surf at r.t.

The good agreement obtained between the theoretical and experimental characterization studies, proves that the theoretical chemistry tools applied are very powerful in order to provide a reliable model to describe the structure of the RuNPs system here synthesized. This work shows that it is possible to develop computational chemistry applied to small nanoparticles with the same level of accuracy and relevance as in molecular chemistry

Roberto González Gómez 135

At the optimal surface composition, the RuNPs showed to have a slightly oxidized surface (ca. 0.5e) according to the pMPA analysis. Better still, with such composition the hydrogen adsorption energy calculated is in the range [-3.1 to -8.0 kcal.mol -1 ] for the (001) & ( 101) planes, which is an important pre-requisite to have promising material for the HER application in the electrolysis of water.

Introduction

Roberto González Gómez 139

3.A Introduction

Metal nanoparticles (MNPs) have been synthetized by following several methodologies and procedures in order to generate novel materials with different sizes, shapes and morphologies, which possess diverse applications, especially in catalysis. A vast range of them has been obtained by changing the synthesis parameters, i.e. metal precursor, reaction media, stabilizing agent, reaction temperature, etc. ([13], [START_REF] Sau | Complex-shaped metal nanoparticles: bottom-up syntheses and applications[END_REF])

In the case of ruthenium nanoparticles (RuNPs), they have been produced with different morphologies going from spherical shape to nanorods. ([89], [START_REF] Ghosh | Nanocrystals, Nanorods and other Nanostructures of Nickel, Ruthenium, Rhodium and Iridium prepared by a Simple Solvothermal Procedure[END_REF]) Also, it has been reported that the synthetic conditions can even change the crystalline structure of RuNPs ranging from face-centered cubic (fcc) to hexagonal close-packed (hcp) structure (figure 3.1) [START_REF] Kusada | Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction Method[END_REF] or even amorphous. [START_REF] Ishiguro | Nanoparticles of Amorphous Ruthenium Sulfide Easily Obtainable from a TiO2-Supported Hexanuclear Cluster Complex [Ru6C(CO)16]2-: A Highly Active Catalyst for the Reduction of SO2 with H2[END_REF] Figure 3.1 HRTEM images of (a) fcc and (b) hcp RuNPs. Insets of decahedral structure and illustration of hcp lattice on the (100) direction, respectively; scales bar 1.0 nm. [START_REF] Kusada | Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction Method[END_REF] The nanoparticles studied and analyzed in this work were synthetized by following the organometallic approach under the same synthesis conditions as shown in chapter II (reaction media, pressure & temperature). The main aim of having the same synthesis procedure was to reduce the variables that can modify the structure and properties of the RuNPs.

Introduction Roberto González Gómez 140

The chosen approach consist in a gradual decomposition of a ruthenium metal precursor ([Ru(COD)(COT)]) by reducing its ligands in the presence of molecular hydrogen (H 2 ), leaving single ruthenium naked atoms, which are quite unstable due to their high surface energy. The ruthenium entities tend to reduce its own instability by suppressing its surface area through a metal agglomeration or by decreasing their surface energy via molecule adsorption or electronic stabilization. [START_REF] Kraynov | Concepts for the stabilization of metal nanoparticles in ionic liquids[END_REF] In fact, the agglomeration phenomenon of nanoparticles is produced by the presence of attractive van der Waals forces, which can be reduced by the presence of ligands acting as obstacles and restricting the coalescence of nanoparticles (scheme 3.1). Thus, the growth of the nanosystems is stopped by the assistance of the stabilizer, which offers either steric and/or electronic protection. [START_REF] Lamey | Impact of organic-ligand shell on catalytic performance of colloidal Pd nanoparticles for alkyne gas-phase hydrogenation[END_REF] Scheme 3.1. MNPs stabilization layer of (a) coordinated ligand and (b) polymer. δ is the adlayer thickness comparison. [START_REF] Lamey | Impact of organic-ligand shell on catalytic performance of colloidal Pd nanoparticles for alkyne gas-phase hydrogenation[END_REF] Hence, the MNPs stabilization and their outcoming properties are highly dependent on their synthesis conditions. Since in this work these variables were reduced at maximum as possible, by using only the organometallic approach with fixed conditions. Then, the influence of the stabilizing agent nature can be truly evaluated.

Considering that the nanosystems properties are very sensitive to all the synthesis conditions, it is preferable to apply only small changes in the synthetic procedure. In this way, the influence of the stabilizing agent on the RuNPs formation and, furthermore in their properties, can be analyzed.

Introduction Roberto González Gómez 141

In chapter II, it was demonstrated that a carboxylic acid with a short alkyl chain length as ethanoic acid (CH 3 COOH) is able to stabilize RuNPs of small size (ca. 1.5 nm). However, it is known from the literature data that in a same family of ligands, those which possess a longer alkyl chain can be better stabilizing agents, [START_REF] Yamamoto | Size-controlled synthesis of monodispersed silver nanoparticles capped by long-chain alkyl carboxylates from silver carboxylate and tertiary amine[END_REF] and also lead to the formation of smaller MNPs. [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF] This is principally due to additionally steric effects induced by the long alkyl chain.

Thus, this chapter is dedicated to study the effect of the alkyl chain length of carboxylic acid ligands on the characteristics of the obtained nanoparticles (size, shape, dispersion, crystalline structure, composition, electronic/surface properties). For this purpose, it has been selected firstly pentanoic acid (CH 3 -(CH 2 ) 3 -COOH) and secondly octanoic acid (CH 3 -(CH 2 ) 6 -COOH) which corresponds to an increase of the alkyl chain length by addition of three and six carbon atoms respectively, comparatively to the ethanoic acid used at the beginning of this PhD work.

Also, in chapter II, it was shown that a theoretical Ru 55 NP model covered by ethanoates and hydrides is very appropriate to describe RuNPs stabilized by the ethanoic entities. This was proven by comparing theoretical and experimental data from complementary spectroscopic characterizations for which a good agreement was reached. Therefore, the same theoretical model will be used in order to study the electronic properties of the novel RuNPs (figure 3.2).

Thus, a similar approach as in chapter II will be followed (combination of experimental and theoretical techniques) in order to fully-characterize the composition, surface state and electronic properties of the obtained RuNPs, and also to determine the influence of a carboxylic acid ligand with a longer alkyl chain length on the properties of the RuNPs. Roberto González Gómez 142

Pentanoic Acid-Capped RuNPs

Stability of metal nanoparticles (MNPs) depends on the nature of the stabilizing agents used for their synthesis because they have a high influence on the nucleation and the MNPs growth rate. The compromise between these two steps is needed to get stable and well-controlled MNPs. ([13], [START_REF] Zheng | One-step one-phase synthesis of monodisperse noble-metallic nanoparticles and their colloidal crystals[END_REF]) Therefore, ligands which are too strongly or too weakly bonded may not be appropriate for stabilizing MNPs when envisaging their use in applications like catalysis.

Taking this information into account and having demonstrated that the ethanoic acid can be used as ligand to stabilize RuNPs, hereafter will be shown a complete characterization of RuNPs stabilized by pentanoic acid, which is slightly longer than ethanoic acid. Presumably this ligand will offer a better stabilization due to the combination of electronic and steric effects.

A main objective of this section was to determine if the expected positive influence of pentanoic acid longer alkyl chain, in terms of stability, could be verified at both experimental and theoretical levels.

Synthesis of RuNPs Stabilized by Pentanoic Acid

The ruthenium nanoparticles (RuNPs) stabilized by pentanoic acid (C 4 H 9 COOH) were synthetized by following the organometallic approach from the stablished procedure described in section 6.1.2.2. Given the study with ethanoic acid showed that stable and homogeneous RuNPs were obtained in the presence of 0. The obtained colloidal suspension of Ru x (C 4 H 9 COOH) 0.4 NPs appeared to be stable for at least one day even without stirring. No precipitate was observed, as a difference from the Ru x (CH 3 COOH) 0.4 NP system where the particles precipitated when stopping the magnetic stirring.

The use of a ligand with a long alkyl chain is known to provide the RuNPs a higher affinity to non-polar solvents. So, one of the properties than can be modulated by changing the stabilizing agent nature is the solubility of the colloidal system. ([232], [START_REF] Jackson | Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayerprotected nanoparticles[END_REF]) The absence of precipitate here observed is thus linked to the influence of the pentanoic acid.

Later on, the colloidal suspension was concentrated to the half volume in order to obtain a drop of the crude concentrated colloidal RuNPs solution to be studied by TEM analysis (see section 6.1. The mean size of the Ru x (C 4 H 9 COOH) 0.4 NPs is ca. 25.2 % smaller than that calculated for the Ru x (CH 3 COOH) 0.4 NPs system (ca. 1.51 nm). Considering that these particles probably have the same crystalline structure (hcp) and using as a reference the magic number for ruthenium clusters, the ratio between the ruthenium surface atoms and the total metal atoms was calculated (see section 6.1.4.1).

As a result, it was found that the Ru x (C 4 H 9 COOH) 0.4 NPs have more than 75.0 % of atoms at their surface. In comparison with the RuNPs stabilized by ethanoic acid, this means an increase of ca. 12.0 % of surface ruthenium atoms. Both RuNPs systems show similar spheroids morphology Roberto González Gómez 145 but the Ru x (C 4 H 9 COOH) 0.4 NPs form a single homogeneous population with a narrower size distribution.

Unsurprisingly from these first results, the pentanoic acid appeared to be a better stabilizing agent than ethanoic acid, leading to smaller and more soluble RuNPs. Several hypotheses can be formulated for explaining this behavior. Among them two stand out which both concern the effect of the ligand on the NP growth process after the nucleation step. The first hypothesis is that the diffusion of the stabilizing agent to the metal entities is fast which can limit/stop the NPs growth process. The second one suggests that the growth is delimited by the surface reaction due to the ligand adsorption. ([234], [START_REF] Thanh | Mechanisms of nucleation and growth of nanoparticles in solution[END_REF]) In both cases, changes in the growth process are put forward as the result of the ligand interaction with the surface of growing particles, showing thus a direct influence on the RuNPs synthesis.

Adsorption Energies Analysis in Ru 55 NP Model Covered by Pentanoic Moieties

To know more about the differences that the stabilizing agent nature can produce on the formation of RuNPs, it is worthy to compare the adsorption energy (E ads ) of the coordinated ligand onto the RuNPs. Thus, an analysis was performed using the previously described theoretical Ru 55

NP model where the same quantity of stabilizing agent was deposed onto the Ru 55 NP (see section 6.2.1). (see section 6.2.2), the corresponding mean adsorption energy of the carboxylic acid entities were calculated (see section 6.2.3).

Considering previous information

Roberto González Gómez 146 As a result, it was found that the mean adsorption energy of ethanoic acid in model I is ca. -51.7 kcal.mol -1 (see section appendix A.4), whilst it was found to be ca. -46.2 kcal.mol -1 for the pentanoic acid case (see section appendix B.1). Since ethanoic moieties have a higher adsorption energy on the ruthenium nanosystems than that of pentanoic entities, and provided that the surface composition is almost the same between the two systems, it seems possible to modulate the electronic properties of the metal core, and hence the catalytic activity of the metal surface, by modifying the carbon chain length.

By taking into account only this data, the model I should be less reactive or more stable than the model II. Given these results are in contrary with the obtained experimentally results (smaller mean size and higher stability observed for pentanoic acid-stabilized RuNPs), other effects have to be taken into consideration, like the electronic barrier produced from the higher steric hindrance generated by the pentanoic acid.

Roberto González Gómez 147

1 H-NMR Study of Ru x (C 4 H 9 COOH) 0.4 NPs

Once the influence of the ligand nature was observed in the RuNPs solubility and in the mean size of the resulting nanosystems, it is reasonably to go deeper in the structural characterization of the novel Ru x (C 4 H 9 COOH) 0.4 NPs. Thanks to the absence of knight shift in these systems [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF] and even more by the presence of an oxygen spacer, [START_REF] Tedsree | Formate as a surface probe for ruthenium nanoparticles in solution 13C NMR spectroscopy[END_REF] the RuNPs can be analyzed by NMR with the primarily objective to observe the stabilizing agent interactions with the RuNPs surface as it was shown in chapter II.

The purified and dried NPs were dispersed in THF-d [START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] and transferred into an NMR tube in order to record a liquid 1 H-NMR spectrum (see section 6.1.3.6). The obtained data was compared with that of the free pentanoic acid for which the characteristic signals are as follows: 33 ppm which can be assigned to the δ and γ protons, of the attached pentanoic moieties, respectively. These assignments can be reasonably inferred from the corresponding peaks of the free pentanoic acid ligand. No other signal can be easily differentiated due to the broadness of the peaks. The small peaks marked with a cross are attributed to impurities that were not possible to eliminate despite the efforts to purify the particles by different cleaning process (see section 6.1.2.2.1). Their identification was not possible even with 2D NMR technique.

At this stage, it is important to note that the absence of any sharp signal between [1.4 & 2.2 ppm] where were expected to find the α and β protons of the carboxylic entity as well as at ca.

ppm (acidic proton), points out the absence of free pentanoic acid in solution and

consequently the closeness of this ligand to the metal surface. [START_REF] Lara | Ruthenium Nanoparticles Stabilized by N-Heterocyclic Carbenes: Ligand Location and Influence on Reactivity[END_REF] Roberto González Gómez 148 In fact, the gradual broadness of the peaks and the absence of some of them given peaks characteristic of free pentanoic acid allow a mapping of the ligand interaction with the RuNPs. ([164], [START_REF] Terrill | Monolayers in Three Dimensions: NMR, SAXS, Thermal, and Electron Hopping Studies of Alkanethiol Stabilized Gold Clusters[END_REF]) Thus, it can be suggested that the pentanoic acid molecules are attached to the RuNPs by their polar head and that the extremity of their alkyl tail clearly has more mobility, meaning that the ligand is not bended on the nanoparticles surface (scheme 3.3). CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 149

DOSY 1 H-NMR Analysis of Ru x (C 4 H 9 COOH) 0.4 NPs

Diffusion-filtered 1 H-NMR spectrum of Ru x (C 4 H 9 COOH) 0.4 NPs (Figure 3.6) revealed the presence of six signals. Among them, the signal at ca. 0.1 ppm is assigned to grease coming from the Shlenk techniques used for the RuNPs synthesis. The signal observed at ca. 3.3 ppm and marked with an "x" is attributed to an artifact derived from the deuterated solvent (THF-d 8 ). It is important to note also that the impurities observed in the 1 H-NMR spectrum in previous section, are not here visible. Consequently, we can anticipate that these species are not directly interacting with the NPs given that they were filtrated by the applied diffusion-filtered 1 H-NMR technique.

The four other signals observed at ca. 0.9, 1.3, 1.6 and 2.0 ppm are assigned to the δ, γ, β and α protons, respectively, of the pentanoic moiety attached at the nanoparticle surface. These attributions were performed by referring to the corresponding signals displayed by the free pentanoic acid. The signal of the α protons of the pentanoic acid at ca. 2.0 ppm was determined by a Gaussian-Lorentzian fitting on the spectrum (L/G = 1.00) but due to its broadness, it could be shifted to both sides of the spectrum compared to that of the free pentanoic acid.

It is important to point out that the sharpness of the described protons is attributed to the protons mobility. Thus, the protons which are farther of the anchoring point (δ & γ) present sharper signals, but it does not mean that they are free in solution. This data supports the absence of bending ligand onto the RuNPs surface.

Roberto González Gómez 150 DOSY-NMR technique is thus widely used for determining if there is free stabilizing agent in solution, or if it is completely attached at the NP surface or a mixture of both situations. In the presence case, since an impurity was observed in the region between [0.5 and 2.5 ppm] , this procedure cannot be done because it will be compromised. But even so the coefficient diffusion of the bigger objects that lies on this region can be obtained.

The measured diffusion coefficient was D = 4.24 × 10 -10 m 2 .s -1 . From this value and considering that the experiment was done at 298 K, a hydrodynamic diameter (D H ) of ca. 2.2 nm was calculated (see section 6.1.3.7.1). In parallel, a sweep of pentanoic acid concentrations in deuterated THF was analyzed by DOSY spectroscopy. As a result, it was found that the D H of pentanoic acid at low concentration and 298 K was ca. 0.6 nm.

Roberto González Gómez 151

By subtracting from the hydrodynamic diameter of the RuNPs the value of the thickness of the ligand layer around the particles (ca. 1.2 nm), the hydrodynamic size of the metal core of the Ru x (C 4 H 9 COOH) 0.4 NPs can be estimated to be ca. 1.0 nm. Comparing with the TEM data where a mean size of ca. 1.1 nm was found for the particles although the difficulty to observe and quantify them, it can be consider there is a good agreement by both techniques. In conclusion, the Ru x (C 4 H 9 COOH) 0.4 NPs are ultra-small with a mean size around 1.0 nm.

Infrared Interpretation of Ru x (C 4 H 9 COOH) 0.4 NPs

Previous FTIR and theoretical studies carried out on ethanoic acid-stabilized RuNPs revealed the presence of the deprotonated carboxylic species at the surface of the nanoparticles and the absence of free ligand. Therefore, after presumably observe the absence of free pentanoic acid in the Ru x (C 4 H 9 COOH) 0.4 NPs ( 1 H-NMR analysis), it is worthy to know if the pentanoic ligands are similarly attached at the surface of Ru x (C 4 H 9 COOH) 0.4 NPs. This information can be obtained by infrared spectroscopy, which will give as a result a better mapping of the RuNPs surface composition.

FTIR data of Ru x (C 4 H 9 COOH) 0.4 NPs was recorded in the ATR mode under inert conditions (see section 6.1.3.3). The obtained spectrum was compared with the experimental characteristic peaks of pentanoic acid [START_REF] Commerce | NIST Standard Reference Database Number 69[END_REF] and THF [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] (figure 3.7).

Roberto González Gómez 152 The FTIR spectrum shows at high wavenumber a broad vibration band at ca. 3300 cm -1 assigned to the stretching vibration modes of water (coming from the RuNPs cleaning process).

The three absorption bands observed between ca. [2950 -2850 cm -1 ] were attributed to the C-H ν as and ν ss vibration modes of the methyl and methylene groups of the alkyl chain of the ligand (CH 3 (CH 2 ) 3 COO(H)). As already seen for the Ru x (CH 3 COOH) 0.4 NPs, no signal is visible in the region [1850 -1600 cm -1 ], meaning the absence of stretching vibration for pentanoic acid (C 4 H 9 C=OOH).

This last observation indicates the absence of the pentanoic acid form (whatever it is free or coordinated) for which signal is expected to be around 1720 cm -1 . [START_REF] Commerce | NIST Standard Reference Database Number 69[END_REF] Rather, the well-defined band present at ca. 1530 cm -1 can be attributed to the ν as vibration mode of the pentanoate (C 4 H 9 C=OO). As it was observed in the RuNPs characterized in the chapter II, the actual interacting moiety onto the RuNPs surface is the deprotonated ligand, pentanoate.

CHAPTER III

Pentanoic Acid-Capped RuNPs

Roberto González Gómez 153

Two other well-separated bands at ca. 1400 and 1260 cm -1 are observed that can be assigned to the asymmetric stretching mode ν as of the carboxylate group (C 4 H 9 C=OO), and the C-H bending asymmetric δ as and symmetric δ s vibration mode of the alkyl chain (CH 3 (CH 2 ) 3 COO).

At lower energy, two strong signals are observed at ca. 1010 and 800 cm -1 . These bands cannot be assigned to any vibrational mode of the pentanoic acid but are quite similar to those of an ether-type molecule. Since THF was used for the purification of the NPs and that THF was proven to be able to interact with RuNPs surface, it can be inferred that these signals correspond to the asymmetric ν as and symmetric ν s vibration modes of coordinated THF (blue signals in figure 3.7). It is reliable to point out the absence of free THF due to these shifted signals. ([238], [START_REF] Bonnemann | The preparation, characterization and application of organosols of early transition metals[END_REF]) Bands at ca. 1094 & 1930 cm -1 (denominated as a and b on the spectrum) can also be attributed to PTHF [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] and CO [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF] , respectively, and can be explained by THF degradation as previously reported.

We can thus conclude from this IR study that in Ru x (C 4 H 9 COOH) 0.4 NPs the interacting ligand with the particle surface is deprotonated and attached under the pentanoate form.

Consequently, the coordination mode of the ligand is the same as previously observed for RuNPs stabilized with ethanoic acid and prepared at the same [ligand]/[metal] ratio of 0.4 equivalent.

However, a significant difference is the clear detection of coordinated THF onto the surface of This phenomenon can be explained theoretically thanks to the mean absorption energies differences between the ethanoic (-51.7 kcal.mol -1 ) and pentanoic acid (-46.2 kcal.mol -1 ). Since the longer alkyl chain moiety has a weaker adsorption energy, the grafting of THF onto the NPs surface can now become more competitive (see section 3.1.2).

Such a difference in adsorption energy can only be related to the influence of the alkyl chain length which is longer by three carbon atoms in the case of pentanoic acid and thus can lead to a more important inductive and steric effects than in ethanoic acid ligand.

FTIR data can also provide interesting information of the electronic charge transmission from the RuNPs to the stabilizing agent (π-backdonation), which is another parameter that can be identified by the vibrational frequencies of the carboxylic moiety. [START_REF] Matito I Gras | Benchmark calculations of metal carbonyl cations: Relativistic vs. electron correlation effects[END_REF] The ν as vibration mode of the ethanoate (CH 3 C=OO) lies at ca. 1545 cm -1 , meanwhile that of the pentanoate (C 4 H 9 C=OO) is found at ca. 1530 cm -1 , meaning that there is a shift of 15 cm -1 to lower wavenumbers for the Roberto González Gómez 154 pentanoate. This shift implies that the retrodonation between the metal and the carboxylate moiety is higher in the pentanoate case. Thus, the stability offered by the pentanoate can be expected to be higher than with ethanoate.

This result agrees with the decreasing of the mean size observed for Ru x (C 4 H 9 COOH) 0.4 NPs (ca. 1.1 nm) vs Ru x (CH 3 COOH) 0.4 NPs (ca. 1.5 nm), but it differs with the mean adsorption energy calculated for the two ligands onto the Ru 55 model (see section 3.1.2) where the ethanoate showed a higher adsorption energy value. But this last theoretical analysis by itself cannot be consider as a conclusive evidence. Even when it can offer some trends, it is necessary to add thermodynamic parameters (T, p, [C]) to make this analysis reliable (see section 6.2.6)

Ligand Coverage Optimization

We have observed that for the same amount of introduced ligand (0.40 equiv.), RuNPs stabilized with pentanoic acid display a smaller mean size (ca. 1.1 nm) than those stabilized by ethanoic acid (ca. 1.5 nm). This result indicates an intrinsic effect of the alkyl chain length on the formation of the nanoparticles and their characteristics, at least their mean size. At this stage of the work, it can be supposed that the longer the alkyl chain the smaller the RuNPs.

However, the differences between the Ru x (C 4 H 9 COOH) 0.4 and Ru x (CH 3 COOH) 0.4 NPs concern by other features than the mean size, i.e. solubility, adsorption energy, retrodonation and THF coordination have been illustrated. These differences in characteristics can arise from two main variables, namely the nature of the capped ligand and the size of the nanoparticles. In order to remove the size variable, a ligand coverage optimization was performed with the aim to obtain with pentanoic acid RuNPs of similar mean size than with ethanoic acid, namely of ca. 1.5 nm

Synthesis of a Series of Ru x (C 4 H 9 COOH) y NPs

It has been reported that the quantity of stabilizing agent added to the NPs synthesis reaction media can have an intrinsic effect on the sizes and morphologies of MNPs. ([205], [START_REF] Carenco | Controlled design of Size-tunable monodisperse nickel nanoparticles[END_REF], [START_REF] Barrière | Ligand effects on the air stability of copper nanoparticles obtained from organometallic synthesis[END_REF])

CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 155

Therefore, a sweep study of the influence of the pentanoic acid quantity added for the RuNPs synthesis was performed (table 3.1), as size control strategy with the aim to find appropriate conditions to get RuNPs of ca. 1.5 nm. Thus, different syntheses of RuNPs were performed by following the organometallic approach with the same procedure described in section 3. The presence of a precipitate was observed for the [1 -3 systems], which can be attributed to the formation of ruthenium bulk and/or, agglomerates or to the difference of solubility of the RuNPs in pentane. Meanwhile, systems [4 -6] remained stable as colloidal suspensions for at least 24 h. These results indicate that for a quantity of ≥ 0.40 equiv. of pentanoic acid added, the colloidal systems of RuNPs formed are soluble in pentane, increasing their solubility on non-polar solvents.

After the RuNPs synthesis a drop of concentrated crude solutions was deposed onto a grid for TEM analysis (see section 6.1.3.1). For systems [1 -3] that presented a precipitate, the drop was taken while stirring vigorously in order to homogenize the solution. Hereafter, it is presented the obtained TEM micrographs and mean size quantification for each novel system.

Roberto González Gómez 156

TEM micrographs recorder for system 1, Ru x (C 4 H 9 COOH) 0.05 , show at first glance the presence of big metal pieces and agglomerates (figure 3.8), which can explain the observed formation of a precipitate.

CHAPTER III

Pentanoic Acid-Capped RuNPs Roberto González Gómez 157

The micrographs obtained for the system 2, Ru x (C 4 H 9 COOH) 0.20 , show the formation of semi-homogeneous nanoparticles that are well-dispersed on the TEM grid and display a mean size of ca. 1.58 ± 0.47 nm (figure 3.10). This mean size is similar to that of Ru x (CH 3 COOH) 0.40 NPs.

However, as it can be seen in the bottom left of the TEM image and in the size histogram, that larger particles are also present which makes this colloidal system to be not a complete homogeneous unidimensional system. For the case of the system 3, Ru x (C 4 H 9 COOH) 0.30 , well-dispersed and small RuNPs were formed with a mean size of ca. 1.47 ± 0.40 nm (figure 3.11). This nanosystem displays a slightly smaller mean size than system 2 but this decrease is judged to be not significant enough given the standard deviation. However, the obtained RuNPs show a better dispersion on the grid and also higher size homogeneity as shown on the size histogram where bigger particles were not found.

This system thus corresponds to a better controlled population of RuNPs that have a quite similar size to those formed with 0.40 equiv. of ethanoic acid (ca. 1.51 nm). This makes this system of RuNPs a good candidate for a direct comparison with the Ru x (CH 3 COOH) 0.40 NPs, as it was looked for.

Roberto González Gómez 158 ). As it was described before, the quantity of stabilizing agent added for the NPs synthesis has a high-influence on the morphology and mean size of the nanoparticles. [START_REF] Ramirez | Influence of organic ligands on the stabilization of palladium nanoparticles[END_REF] Also, at this point it can be illustrated that lower quantity of pentanoic acid can stabilize the same mean size of RuNPs than that needed by using ethanoic acid as ligand. In conclusion, these observations are another evidence of the better stabilization properties that possess a longer alkyl chain ligand vs a shorter one.

According to the previous observations, it is worth to know more about the impact on RuNPs mean size, while it is exposed to higher quantity of pentanoic acid ≥ 0.40 equiv.

System 5, Ru x (C 4 H 9 COOH) 0.50 , presents RuNPs with a mean size of ca. 1.18 ± 0.18 nm (figure 3.12). These RuNPs appear to be quite similar to those of system 4, showing the same morphology and no statistical difference in the mean size. Thus, it is probably that smaller NPs than ca. 1.1 nm cannot be obtained even if a higher quantity of pentanoic acid is added to the setup used for the RuNPs synthesis, forming a plateau. [START_REF] Guerrero | Efficient Ruthenium Nanocatalysts in Liquid -Liquid Biphasic Hydrogenation Catalysis : Towards a Supramolecular Control through a Sulfonated Diphosphine -Cyclodextrin Smart Combination[END_REF] Roberto González Gómez 159 Hereafter, it is presented an extract of the RuNPs mean sizes and size dispersion according to the TEM analyses (table 3.2). Where it can be observed the similarities between some systems, and that the addition of more stabilizing agent for the RuNPs synthesis will render to smaller nanosystems.

CHAPTER III

Pentanoic Acid-Capped RuNPs

Roberto González Gómez 160 In summary, the study performed by a sweep of pentanoic acid concentration, used for the synthesis of RuNPs, evidences three different groups of colloidal systems. First, the formation of a heterogeneous system composed by a mixture of RuNPs, agglomerates and bulk material was observed when adding 0.05 equiv. of the ligand. The second group gathers the nanoparticles synthetized with [0.20 and 0.30 equiv.] that have primarily the same mean size, ca. 1.5 nm, although slight differences were observed. Finally, the third type of RuNPs corresponds for the minimum NPs size obtained, ca. 1.1 nm, which corresponding to the RuNPs stabilized by [0.40 -0.60 equiv.] of pentanoic acid (table 3.3). This study is based on changing the quantity of stabilizing agent in order to have different types of RuNPs, which as was expected can display different mean sizes. But also, whit this analysis, it was seen than it is possible to obtain similar RuNPs with different quantity of added ligand, as it was seen for the group 2 & 3. This phenomenon could indicate that the particles can have a higher ligand surface coverage without changing the morphology or their size.

CHAPTER III

Pentanoic Acid-Capped RuNPs Roberto González Gómez 161

It is also noteworthy that a lower quantity of pentanoic acid than of ethanoic acid has allowed to get RuNPs of ca. 1.5 nm. This highlights the higher capacity of pentanoic acid to stabilize RuNPs compared to the ethanoic counterpart. This result confirms the previous presented hypothesis about the influence of the alkyl chain length of the carboxylic acid ligands in their efficiency to stabilize RuNPs.

From all these results, it can be concluded that the quantity of pentanoic acid introduced for the nanoparticle synthesis has an influence on their formation and that this parameter is a way to have at disposal stable populations of RuNPs of ca. [1.5 or 1.1 nm], displaying the same ligand at their surface.

Another important point is that the ligand amount around the particles can also vary for a

given mean size (in the ranges [0.20 -0.30 equiv.] and [0.40 -0.60 equiv.] for 1.5 and 1.1 nm, respectively). Given that the objective was to have in hands RuNPs of ca. 1.5 nm for comparison studies with the most stable ones got with ethanoic acid (Ru x (CH 3 COOH) 0.40 ), RuNPs from group 2 are convenient.

According to the literature, the electronic stability of the NPs depends on the ligand coverage, namely, a lower ratio leads to a lesser stability. [START_REF] Yu | Formation and stability of size-, shape-, and structure-controlled CdTe nanocrystals: ligand effects on monomers and nanocrystals[END_REF] Therefore the NPs prepared with 0.30 equiv. of pentanoic acid (Ru x (C 4 H 9 COOH) 0.30 ) that form a more homogeneous population of RuNPs than those prepared with 0.20 equiv. appear to be the best NP system for comparison studies with Ru x (CH 3 COOH) 0.40 NPs.

NMR Analysis of Ru x (C 4 H 9 COOH) y NPs

In this section, is presented a comparative 1 H NMR study performed on the series of pentanoic acid-stabilized RuNPs prepared with different quantities of ligand, as described in previous section 3.1.6.1. The objective of this study was to get information on the interacting ligand at the ruthenium surface (seen as broad signals) and also, to evidence the presence of free ligand (seen as sharp signals).

The proton NMR data (figure 3.14) were recorded as described in section 3.1.3, but from the crude colloidal solutions (the nanoparticles were not purified but just redissolved in Roberto González Gómez 162 deuterated THF after evaporation of pentane, the same concentration of RuNPs was fixed by using the same volume of deuterated solvent for all systems studied for comparison purpose). The signals attributed to side products are marked with an "x".

Peaks assigned to a and b protons of the pentanoic acid can be seen as broad signals in all the spectra. The intensity of these peaks increases as the result of the increasing quantity of the ligand (see spectra 1 to 6, corresponding to 0.05 to 0.60 equiv. of added ligand). The signal assigned to the c protons of pentanoic acid can be observed as a broad peak for the RuNPs systems stabilized by 0.30, 0.50 and 0.60 equiv. of pentanoic acid (spectra 3, 5 and 6), meaning that probably their alkyl chains are more elongated and therefore it can be seen in contrary of what is observed for systems 2 and 4.

Finally, the peak attributed to the d protons of pentanoic acids is not observed for the RuNPs stabilized from [0.05 to 0.50 equiv.] of pentanoic acid, but it is for those prepared with 0.60 equiv. (see red circle). The observation of this signal for RuNPs stabilized with 0.60 equiv. indicates the presence of free ligand. Indeed, protons in the proximity of the metal surface are not expected to be visible due to important broadening as previously explained, which is the case for d protons that are very close to the carboxylic group interacting with the metal surface (α protons). Thus, the fact they are visible can only be explained by the presence of free ligand in solution.

As a conclusion of this [START_REF] Züttel | Hydrogen as a Future Energy Carrier[END_REF] H NMR study, it can be inferred that the only RuNPs system that clearly presents free ligand is Ru x (C 4 H 9 COOH) 0.60 . For the other pentanoic acid-stabilized RuNPs the whole ligand is suspected to be in complete interaction with the RuNPs, according to the absence of the α protons of the ligand denoted as "d" in the spectra.

Roberto González Gómez 163 recorded for RuNPs from the 3 different groups (see classification in section 3.1.6.1) that were prepared with 0.05 equiv. (group 1; brown), 0.30 equiv. (group 2; green) and 0.60 equiv. (group 3; purple) of pentanoic acid ligand. As a reminder, these spectra were obtained from the crude colloidal solutions and side products can be observed (marked as "x"). However, the THF deuterated solutions were prepared with a same concentration which allows to make a trustworthy comparison by stablishing the THF as a reference.

Roberto González Gómez 164

From this figure, it can be seen that the broadness of the spectra increases with the quantity of ligand. This can imply that RuNPs from group 3 have higher quantity of ligands interacting with ruthenium surface than those of group 2 and even more group 1. The experiment has shown that the only system that display the presence of free pentanoic acid is the Ru x (C 4 H 9 COOH) 0.60 NPs. Also, it has been demonstrated the difference in the amount of ligand interacting with the nanoparticle surface by looking at the broadness of the different groups found by TEM analysis.

From this observation and by making a parallel between the amount of added ligand and the size of the RuNPs obtained, one hypothesis could be that the higher the quantity of stabilizing agent, the higher the interaction with the metal surface, and the smaller the RuNPs formed.

To corroborate this hypothesis, a similar analysis was performed but looking at the spectra of RuNPs that belong to the same group (2). Hereafter, it is presented the compared spectra As a reminder, by TEM analysis it was observed that a higher quantity of ligand led to smaller NPs until reaching a plateau at size ca. [1.0 -1.1 nm]. From 1 H NMR studies, it was detected that only at 0.60 equiv. of pentanoic acid, free ligand is visible. Also, higher is the quantity of stabilizing ligand added, higher is the amount of ligand interacting with RuNPs. In order CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 166

to get more information of the ligand layer around the RuNPs, DOSY NMR studies were performed.

DOSY NMR studies can provide more insights about the possible presence of free ligand into the NPs system, but since as observed in figure 3.14 the broad region assigned to the ligand attached at the NP surface ([0.5 -2.5 ppm]) is corrupted by the presence of side products ("x"), it is not a trustworthy analysis (figure 3.14). However, the hydrodynamic radio (r H ) for the largest objects (NPs + ligand) can be obtained and compared with size data resulting from TEM studies. These analyses will disperse the possible doubts that could be generated form the TEM analyses due to the NPs small mean sizes.

Hydrodynamic diameters (D H ) given in table 3.4 for each system of NPs analyzed were obtained from the recorded diffusion coefficients of the large species observed, at r.t. in deuterated THF solution (see section 6.1.3.6.1). As it can be seen, except for the first system (no homogeneous NPs formed), the diffusion coefficient increases while the quantity of ligand used for the RuNPs synthesis augments. As a consequence, the calculated size of the objects shows a gradual decrease. Such a phenomenon was not noticed by TEM analysis where the NPs were gathered in size groups. However, these size data need to be taken carefully because the estimated random error in DOSY measurements (signal/noise) could rise to 8.0 % and it can increase even more depending on the experimental treatment and equipment used for the analysis. [START_REF] Thrippleton | A fast method for the measurement of diffusion coefficients: One-dimensional DOSY[END_REF] Table 3.4 DOSY analyses performed on a scope of RuNPs stabilized by different quantity of pentanoic acid with their corresponding diffusion coefficients, calculated hydrodynamic diameter and estimated size RuNPs species. The following spectrum presents only broads signals. The biggest ones correspond to THF, a solvent used in the RuNPs silica dilution. Moreover, there is also a signal at ca. 12 ppm that can be attributed to the methyl group of the pentanoic acid. This methyl peak was not observed for the Ru x (CH 3 COOH) 0.4 NPs pointing out a difference in the methyl group proximity to the RuNPs surface for the two systems of NPs. This could be expected because the pentanoic acid has a longer alkyl chain length than ethanoic counterpart which can make the methyl group far from the metal surface if there is no chain folding towards the NP surface. This methyl group being visible means the extremity of the alkyl chains is not interacting or even close to ruthenium surface.

System

The most important peak is the one found at low field at ca. 188 ppm, that can be assigned to carboxylic moiety interacting with the NP surface in comparison to the free pentanoic acid that displays a signal at ca. 174 ppm (figure 3.17 bottom bars) for this carbon.

It is important to note that no signal is visible in the [170 -180 ppm] range, indicating that there is no free pentanoic acid in the sample. The difference in chemical shift between coordinated and free pentanoic acids is more than 10 ppm of deshielding, which is in agreement with previous data obtained for ethanoic acid-stabilized RuNPs ( 186 vs. 172 ppm for coordinated and free ethanoic acid (solution), respectively). This phenomenon was attributed to the coordination of the carboxylic moiety onto the RuNPs as deprotonated specie.

CHAPTER III

Pentanoic Acid-Capped RuNPs Roberto González Gómez 170

As a result, it can be concluded that for Ru x (CH 3 COOH) 0.4 NPs, the ligand is also deprotonated and coordinated under the form of pentanoate. Considering that all the reported carbon should come from the pentanoic acid, then the quantity of oxygen can be estimated to 11.9 % of sample weight which would lead to 38.0 % of organics in the sample and consequently 62.0 % of ruthenium metal content. When calculating to molar equivalents, it can be observed that around 0.6 equiv. of pentanoic acid are surrounding the RuNPs, which is impossible according to the added ligand (0.3 equiv.).

It is thus clear that another source of carbon (pollution) should be the responsible of increasing the carbon content onto the RuNPs surface. This phenomenon was attribute to the coordination of THF, which was observed by FTIR analysis (see section 3.1.5). Thus, THF have a high influence on the elemental analysis determination. Thus, the same Ru 55 NP model was used as computational strategy for the DFT titration of the novel Ru x (C 4 H 9 COOH) 0.3 NPs, with the aim to evaluate the quantity of hydrides and pentanoates surrounding the RuNPs. The results can clarify some previous posed inquiries like the low amount of hydrides present in these systems vs another RuNPs [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] or the quantity of carboxylate capping ligand that could stabilize RuNPs depending its alkyl length chain.

Hence, the Ru 55 NP model was covered by different co-adsorbed quantities of hydrogen and pentanoates, assuming an easy O-H activation, as evidenced by FTIR and solid-state NMR experimental analysis. With now large surface ligands, and since the computational cost of DFT calculations is roughly proportional to N 3 (N being the number of atoms) it is necessary to be as efficient as possible.

Therefore, this DFT titration process was performed by using the previous data obtained for the Ru x (CH 3 COOH) 0.4 NPs system where it was seen a low hydride coverage value and a high amount of ethanoates (figure 3.18). This was possible since FTIR and solid-state NMR spectroscopy results pointed out toward a stabilization of the RuNPs by pentanoates.

Roberto González Gómez 173 Thus, ten different coverage possibilities have been considered, with a systematic geometry optimization (table 3.7). The surface compositions were set up with a high quantity of pentanoates (between [8 -16]) and a rather low quantity of hydrides (between [8 -33]). Details on the DFT energies of the optimized structures are reported in sections appendixes A. By using the ab initio thermodynamic methodology, the Gibbs free energies (Δ a G°) were calculated for the ten structures at 300 K, considering the ligand-metal vibration corrections (see section 6.2.7 and appendix D) used for the ethanoic acid DFT titrations. This approximation can be done due to the stronger influence on the Δ a G° value for the Ru-H vibration modes than that of Ru-carboxylate. ).

Only two of the ten studied structures (66 & 59) are not stable in any range of the presented phase diagram. The analysis shows that the previous approximations performed to reduce the computational resources used for this study were appropriated (low quantity of hydrides and high amount of carboxylates). Because, the stables structures found in the phase diagram reliable domains ([10 -10 to 10 1 ] M & bar) presented more pentanoates than the lowest computed system (≥ 8 C 4 H 9 COO) and the quantity of hydrides was tending to zero (≤ 16 H).

The pentanoic acid concentration domain relevant with respect to experiments can be estimated by calculating the pentanoic acid concentration added for the Ru x (C 4 H 9 COOH) 0.3 NPs synthesis. Since this study is considering the species in equilibrium, it was assumed that all the pentanoic acid remains in the NPs, the obtained concentration was ca. 10 -2.9 mol.L -1 . The hydrogen reliable range was considered to be similar as calculated from Ru x (CH The most stable structure in the described range, presents as capped ligands 14

pentanoates and 14 hydrides raised from the carboxylic acid deprotonation (figure 3.19, domain 63). The other stable structure has additional 17 H coming from the reaction media, but this structure was found in a small domain of the delimited phase diagram (experimental conditions).

The stabilizing agent vs metal surface atom ratio was found to be 0. confirm the low quantity of hydrides present at the surface of carboxylic acid capped-particles compared to other ligand-capped RuNPs. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Table 3 state that the quantity of carboxylic acids needed to stabilize the same mean size of nanoparticles will depend on its alkyl chain length. For further comparison between these systems, it is thus necessary to take into account that there seems to be a correlation between the alkyl chain length and the quantity of ligands capping the NPs Finally, this theoretical titration confirms that a low quantity of hydrides is surrounding the nanoparticle, i.e. 0.3 to 0.6, to be compared to the usually found 1.3 H/Ru surf . [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Meaning that RuNPs synthetized by using carboxylic acids as stabilizing agent will have as structural property a low amount of hydrides.

Theoretical Catalytic Assessing: HER Reaction

Electronic stability of the nanosystems depends on the coverage rate by the stabilizing agent and of its adsorption energy. It has been reported that the lower the capping ligand/metal can be correlated ratio, the lesser the NP stability. But this relation also depends on the steric hindrance of the stabilizer which interacts with the MNPs surface due to the ligand barrier that is formed. ([205], [START_REF] Yu | Formation and stability of size-, shape-, and structure-controlled CdTe nanocrystals: ligand effects on monomers and nanocrystals[END_REF])

CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 178

It is well-known that metal nanoparticles and specially RuNPs have a good affinity for hydrogen, their catalytic performance in several reduction reactions is also recognized, with easy adsorption and desorption of hydrogen onto the RuNPs surface. ([59], [START_REF] Zhao | Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties[END_REF])

As it was reported in section 2.7, it is possible to evaluate the potential catalytic activity of RuNPs in the hydrogen evolution reaction (HER) by following the seminal work of NØrskov. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] It is based on the correlation of the H adsorption energy (ΔG H ) that can be correlated with the exchange current in the HER reaction, (after the empirical addition of 5.5 kcal.mol As can be seen in table 3.9, it is not easy to conclude about the relative performance of ethanoic acid-and pentanoic acid-stablized RuNPs regarding HER. On some sites, the theoretical analyzed Ru 55 NP covered by pentanoates shows lower affinity to hydrogen than the Ru 55 NP capped by ethanoates (table 3.9). This study should be completed by considering another arrangement of surface ligands and a slightly different coverage value, but it seems however that CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 180

the carboxylic alkyl chain length may have an influence on the HER catalytic reaction. As a result, it is probable that RuNPs covered by pentanoates may be more active for the hydrogen production than its ethanoates-stabilized counterpart

Conclusion

In the first part of this chapter, it was explored the possibility to stabilize RuNPs with a carboxylic acid of longer alkyl chain length, by changing from ethanoic to pentanoic acid. In order to make a reliable comparison study the same amount of ligand was first considered for RuNP synthesis, Ru x (C 4 H 9 COOH) 0.4 . The obtained nanosystem has shown a better solubility in non-polar solvent than that stabilized by ethanoic acid and also a smaller mean size of ca. 1.1 nm vs. 1.5 nm, respectively. These results were a first evidence of the influence of the nature of the carboxylic acid on the properties of the RuNPs.

NMR studies performed on Ru x (C 4 H 9 COOH) 0.4 NPs have shown that the ligand added to the reaction media is fully interacting with the nanoparticle surface due to the absence of visible free ligand. Also, it was noticed that the alkyl chain of the pentanoic species is not folded at the metal surface (protons of methyl groups were clearly observed). It can thus be proposed, that the ligand is attached in an extended way given certain mobility to the tail of the stabilizing agent. DOSY analysis has shown the presence of broad signals in the range of the expected peaks of the ligand and the hydrodynamic diameter calculated from diffusion coefficient measured agrees with the mean size of the NPs determined by TEM analysis.

The FTIR analysis allowed to confirm the pentanoic acid deprotonation in the resulting RuNPs. The signal of a carboxylate moiety was seen but not that expected for a carboxylic acid CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 181 moiety (free or coordinated). Also, it was observed by this technique the presence of THF and its probable degradation into CO and PTHF.

Even when the adsorption energy of the pentanoic acid onto the Ru 55 NP model (-46.2 kcal.mol -1 ) appeared to be smaller than that of ethanoate (-51.7 kcal.mol -1 ), the FTIR spectroscopy has exhibited higher retrodonation of the ruthenium metal surface to the pentanoic moiety than for the compared Ru-ethanoate system, as observed by the shift towards lower wavenumber of the carboxylate band.

As a first general conclusion, it can be said that changing the alkyl chain length by three carbons from ethanoic to pentanoic acid provides better solubility in non-polar solvents, smaller NPs and improved homogeneity. Therefore, it can be considered that pentanoic acid is a more suitable stabilizing agent than ethanoic acid.

Then with the aim to reduce the mean size variable and make a more reliable comparison for these RuNPs, a sweep of pentanoic acid quantity introduced for the NP synthesis was performed (from [0.05 to 0.60 equiv.]/[Ru]). This allowed to evidence that NPs of mainly two different sizes can be synthetized (ca. 1.1 and 1.5 nm) by changing the amount of the added stabilizing agent (TEM analyses). Moreover, proton NMR studies showed that NPs of similar mean sizes can have different rates of ligand surface coverage.

From the results on the influence of the ligand amount on the size of the particles, the system Ru x (C 4 H 9 COOH) 0.30 system was chosen because of its higher homogeneity and similar mean size than Ru x (CH 3 COOH) 0.4 NPs (ca. 1.5 nm) for a deeper comparison. The fact that a 0.3 equiv. of pentanoic acid allowed to stabilize NPs of same size as 0.4 equiv. of ethanoic acid pointed out the better stabilizing properties of the pentanoic vs ethanoic acid.

Solid-state NMR study performed on Ru x (C 4 H 9 COOH) 0.3 NPs confirmed the deprotonation of the pentanoic acid and its interaction with the ruthenium surface as pentanoate. Taking this into account and previous information from chapter II a DFT titration of surface ligands has been performed. As a result, it was found that the most stable structure according to the experimental synthetic variables is Ru 55 (C 4 H 9 COO) 14 (H) 14 , which showed a lower quantity of capping ligand than that determined for the Ru x (CH 3 COOH) 0.4 system, Ru 55 (CH 3 COO) 16 (H) 16 . This result also corroborated that the pentanoic acid has better stabilization characteristics than ethanoic acid.

CHAPTER III

Pentanoic Acid-Capped RuNPs Roberto González Gómez 182

Finally, the evaluation of Ru 55 (C 4 H 9 COO) 14 (H) 14 system for the HER reaction highlighted that the RuNPs stabilized by pentanoic acid can probably have a better performance in the hydrogen production than those capped by ethanoic acid.

To conclude this first part of chapter III, changing the alkyl chain length by three carbons from ethanoic to pentanoic acid provided RuNPs smaller in size at a lower [ligand]/[Ru] ratio, more homogeneous in size/shape, less crowded and probably more interesting for the catalytic HER reaction. Therefore, to sum up, it can be considered that pentanoic acid is a more suitable stabilizing agent than ethanoic acid.

In order to better understand the influence of the alkyl chain length on the RuNPs properties. The synthesis of RuNPs with octanoic acid will be presented.

Octanoic Acid-Capped RuNPs

Metal nanoparticles (MNPs) can be modulated by changing several factors i.e. synthesis methodology, temperature, ligand nature, quantity of stabilizing agent, reaction time, etc. ([246], [START_REF] White | Supported metal nanoparticles on porous materials. Methods and applications[END_REF])

Specially for ruthenium nanoparticles (RuNPs) synthetized by the organometallic approach, they can be tuned by modifying the nature of the stabilizing agent, the reaction media and the reductive gas pressure applied. ([97], [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF])

In the literature, the influence of the stabilizing agent nature in dictating the size, shape and interparticle spacing, is described. [START_REF] Grubbs | Roles of polymer ligands in nanoparticle stabilization[END_REF] In general, the capping ligands modify the internal electronic properties of the systems and moreover the interactions between the nanosystems and its surroundings, in other words the possible interfaces among the media and the MNPs. [START_REF] Lin | Nanoparticle assembly and transport at liquid-liquid interfaces[END_REF] Previously, the differences obtained in the RuNPs synthetized by carboxylic acid with different alkyl chain length (solubility, size, dispersion, etc.) were demonstrated (see section 3.1).

In fact, it was observed that these characteristics can be modulated by modifying the quantity and type of stabilizing agent.

Roberto González Gómez 183

Compared to previous results obtained with ethanoic acid, it appeared that the alkyl chain of this acid has an influence on the stabilization efficiency and also on the characteristics of the particles. Indeed, pentanoic acid-stabilized nanoparticles were more soluble in pentane, more homogeneous in size/shape and with a smaller size at a lower [ligand]/[Ru] ratio, and also potentially of higher interest for HER reaction than those prepared with ethanoic acid.

Since the high impact on increasing the alkyl chain length of the carboxylic acid ligands for obtain RuNPs was demonstrated, now the synthesis of similar RuNPs but stabilized by a longer carboxylic acid is going to be studied. Octanoic acid will be the analyzed molecule which is a saturated moiety that has three carbons more than the previous studied ligand. The obtained results are described in the second part of this chapter.

Assisted-Synthesis of RuNPs Stabilized by Octanoic Acid

Metal nanoparticles (MNPs) can be synthetized by using several ligands and procedures, but there are cases when the nanosystems cannot be formed unless there is a synthesis assistant.

For the formation of the MNPs, the use of solution-assisted methodologies i.e. sol-gel, hydrothermal, etc., are well-known. [START_REF] Subramanian | Alcohol-assisted room temperature synthesis of different nanostructured manganese oxides and their pseudocapacitance properties in neutral electrolyte[END_REF] In fact, the use of alcohols and polyalcohols has been widely applied for synthetize metal and, even more, ruthenium nanoparticles (RuNPs). [START_REF] Li | Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane[END_REF] THF is a recurrently used solvent for the synthesis of ruthenium-based nanoparticles.

Apart from being an appropriate solvent to solubilize the Ru(COD)(COT) complex used as ruthenium source and the organic ligands used as stabilizers, some works have also shown that THF can assist the stabilization of the NPs formed. In fact, being an ether, THF can coordinate at the surface of RuNPs through the oxygen atom. NMR studies have evidenced that THF can release from the surface of ligands-stabilized Ru NPs. [START_REF] Pelzer | Organometallic Synthesis of Size-Controlled Polycrystalline Ruthenium Nanoparticles in the Presence of Alcohols[END_REF] However, THF alone is not able to stabilize homogeneous small RuNPs leading to a mixture of nanosystems and agglomerates (see section 2.5.3). That is why THF can be considered as a stabilizing assistant for metal NPs.

Thus, preliminary studies for the synthesis of RuNPs in the presence of octanoic acid were performed by following the organometallic approach (see section 6.1.2.2), but with the difference of using THF as solvent in order to improve the morphology homogeneity of the formed RuNPs Octanoic Acid-Capped RuNPs Roberto González Gómez 184 (scheme 3.4). Another parameter to take into account was the reaction time, that in these cases was left around 15 h to assure the complete ruthenium metal precursor decomposition. Previous obtained information about the synthesis of RuNPs stabilized with carboxylic acids, was considered as the starting point for the synthesis of these nanosystems. Therein, it was observed the formation of semi-homogeneous and homogeneous RuNPs by adding 0.4 equiv. of ethanoic and pentanoic acid, respectively. Therefore, a similar formula ((Ru x (C 7 H 15 COOH) 0.4 ) THF )

was applied as point of departure for analyzing these systems, aiming to determine the influence of the assisted-solvent.

Aiming The colloidal solution was then concentrated to the half volume for slightly increase the concentration of RuNPs, aiming to obtain a concentrated drop of the crude colloidal synthetized RuNPs to be studied by TEM microscopy (see section 6.1.3.1).

The obtained micrographs display the formation of small RuNPs which can be easily As reported in other words, the THF solvent-assistance produced an increase in the RuNPs morphology but its effect in reducing the NPs mean size seems to be unfavorable. As it can be seen in the previous table, the mean size of the RuNPs tend to decrease as a function of the alkyl length chain, but it was observed a higher effect for the RuNPs stabilized with pentanoic acid. Also, the size distribution is higher for the RuNPs formed with octanoic acid, making the THF a poor solvent-assistance at least in this type of RuNPs synthesis.

After the TEM analysis, the crude colloidal solution was purified by several pentane-THF washing cycles. The NPs were thus obtained under the form of a fine black powder.

In order to know more about the THF role in the synthesis of RuNPs or try to explain the observed data in TEM microscopy, a FTIR analysis was performed after dispersion of the purified nanoparticles into dry KBr (using P 2 O 5 as desiccant; see section 6.1.3.3) and preparation of a pellet.

All the procedure was carried out under argon, in a glove-box. The FTIR data obtained for the (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs in KBr are compared to the representative peaks of octanoic acid [START_REF] Arivazhagan | Dielectric, FT-IR and UV-vis spectroscopic studies on the fluid structure of diisopropyl ethercaprylic acid mixture[END_REF] and THF [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] in the figure 3.23.

Roberto González Gómez 187 The so-obtained infrared spectrum does not show any signals above 3000 cm -1 . This indicates the absence of water or any O-H stretching vibration mode, but the absence of free or coordinated octanoic acid cannot be completely discarded. Three well-separated signals can be observed at ca. 2980 -2850 cm -1 that were attributed to the C-H ν as and ν ss vibration modes of the alkyl chain (CH 3 (CH 2 ) 6 COOH). ). Between 1850 and 1600 cm -1 which is the expected area to observe the specific signals of carboxylic acids, a clear signal is visible at ca. 1710 cm -1 together with a left shifted shoulder at ca. 1730 cm -1 . This could be due to the presence of different carboxylic acids and this contrasts with FTIR observations done on previous systems of RuNPs stabilized with carboxylic acids bearing shorter alkyl where only one band for coordinated carboxylate was detected.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 188

Thus, it can be suggested two different hypotheses related to these bands: They could correspond to two different coordination modes of octanoic acid onto the RuNPs surface or the most probable scenario could be that the first signal (shoulder) is attributed to free octanoic acid (reference region [START_REF] Arivazhagan | Dielectric, FT-IR and UV-vis spectroscopic studies on the fluid structure of diisopropyl ethercaprylic acid mixture[END_REF] ) and the second to the coordinated carboxylic acid moiety. Anyway, both hypotheses involve as a conclusion the presence of stabilizing agent excess into the system.

Another sharp and even stronger signal is present at ca. 1533 cm -1 was assigned to the ν as vibration mode of deprotonated octanoic acid in interaction with the surface of the RuNPs (C 7 H 15 C=OO). In other words, this band seems to be the signature of the octanoate form of the stabilizing ligand, as already observed for previous systems of carboxylic acid-stabilized RuNPs.

Other bands between 1500 and 1250 cm -1 could be easily assigned to the asymmetric stretching mode ν s of the carboxylic group (C 4 H 9 C=OO(H)) as well as to the C-H bending asymmetric δ as and symmetric δ s vibration modes of the alkyl chain (CH 3 (CH 2 ) 3 COO).

Also, a band commonly observed for organic compound containing more than four linked methylene groups ( ρ(CH 2 ) n ) can be found at 720 cm -1 . Two narrow bands at ca. 1021 and 801 cm -1

were attributed to coordinated THF as already observed for previous systems of carboxylic acid-stabilized RuNPs systems purified by THF-washing. It is worth to notice that even when the solvent used for the nanosystems synthesis was THF there is no signals that can be assigned to free THF. ([238], [START_REF] Bonnemann | The preparation, characterization and application of organosols of early transition metals[END_REF])

Also, peaks named a and b on the spectrum can be attributed to THF derivatives: the a band at ca. 1100 cm -1 can be assigned to PTHF [START_REF] Deng | Real-time monitoring of ring-opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy[END_REF] originated from its own polymerization and the b bands at 2060 and 1995 cm -1 to CO coming from the solvent decarbonilation. [START_REF] Martínez-Prieto | A betaine adduct of N-heterocyclic carbene and carbodiimide, an efficient ligand to produce ultra-small ruthenium nanoparticles[END_REF] These observations show the reactivity of THF at the RuNP surface as previously seen with other systems of NPs prepared by the organometallic approach.

To summarize the most important information of this FTIR analysis, it can be mentioned that it evidenced three different signals corresponding to asymmetric carboxylic vibration modes which indicate the presence of at least three different types of molecules interacting with the ruthenium surface. On the basis of previous results obtained in chapter II and section 3.1, it can be proposed that the  as (COOH) vibration band at ca. 1533 cm -1 corresponds to the octanoate form of the stabilizing ligand. The other two bands may result from a ligand excess that would interact with the metal surface as carboxylic acid or its free state.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 189 The second region shows at ca. 1530 cm -1 a carboxylate vibration band assigned to the deprotonated stabilizing agent (carboxylate form of the stabilizing ligand) for each case of carboxylic acid-stabilized RuNPs. However, the spectrum of the RuNPs synthesized with octanoic acid displays two other carboxylic vibration bands attributed to the protonated ligand in contrast to the two other cases. This may be explained by a ligand excess due to the longer alkyl chain length of the ligand or the presence of THF as solvent.

Finally, the last highlighted zone (green) that correspond to the R-O-R vibration area evidenced the presence of coordinated THF with differences observed in terms of intensities.

Roberto González Gómez 190 Previously, the retrodonation observed between the ruthenium atoms and the coordinated ligand was used as a stabilization parameter. For instance, previous studies have evidenced that the RuNPs stabilized by pentanoic acid have presented a lower vibrational energy in the deprotonated carboxylic vibration compared to RuNPs synthetized with ethanoic acid (1530 vs 1545 cm -1 ), meaning a better stabilization. However, for the case of RuNPs prepared with octanoic acid, the carboxylate band is seen at a similar wavenumber than for the pentanoate case (1533 vs 1530 cm -1 ). This result indicates that the interaction of the dimetallacycle formed at the RuNP surface by octanoates is quite similar to that of dimetallacycle from pentanoate (figure 3 It is worth to notice that in the area corresponded for the methyl group [0.8 -1.0 ppm] there is a decrease of the bottom broadness and the peaks attributed for this signal are sharper than others. Thus, it can be said that the coordinated ligand is not bended onto the NPs surface and its tail posses higher dynamism. The conbination of these spectroscopic techniques can offer information on the RuNPs surface state, where it can be clearly observed for the fist time in this work the presence of free and coordinated ligand. In other words, the presence of THF as a solvent and the longer alkyl chain legnth of the octanoic acid has as a consequence a better nanosystem stabilizitation and therefore CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 193 an excess of ligand can be observed by adding the same quantity of stabilizng agent into the RuNPs synthesis ([ligand]/[metal] ratio 0.4 equiv.).

Theoretical Determination of Adsorption Energies of Carboxylic Acids onto Ru 55 Model

In previous section 3.2.1, it was described the synthesis of RuNPs in the presence of 0.4 equiv. of octanoic acid and THF as a stabilizer and a solvent, respectively. It was observed a decrease of the RuNPs mean size when a longer alkyl chain length ligand was used for the RuNPs synthesis, but a direct trend was not found.

FTIR and 1 H-NMR data revealed the presence of octanoate and/or octanoic acid coordinated at the ruthenium surface together with the presence of free octanoic acid. The later point indicated the presence of a ligand excess. FTIR data also indicated the presence of coordinated THF at the RuNPs surface, as well as its reactivity as seen by the detection of CO bands. Moreover, when comparing the FTIR characteristics of the RuNPs prepared with ethanoic acid and pentanoic acid, it was observed an increase of π-backdonation with pentanoic acid system vs ethanoic acid system. Such an increase was not detected between the octanoic and pentanoic acid stabilized nanosystems. This could result from similar behavior and adsorption energy (E ads ) of these ligands onto the surface of RuNPs.

Thus, the highlighted question is which is the real role of the THF in the synthesis of RuNPs? This section will be dedicated to theoretical studies aiming at understanding the behavior of THF at the NP surface. Adsorption energies will be calculated (see section 6.2.3) by attaching the three carboxylic acids studied (ethanoic, pentanoic and octanoic acid) onto the Ru 55 NP model (see section 6.2.1). Different carboxylic coverage values will be studied in order to exclude the THF variable.

The carboxylic moieties were settled on the Ru 55 NP under the form of carboxylates, owing to the information obtained from previous experimental and theoretical studies. For each RuNPs system of RuNPs, ten, twelve and fourteen carboxylate molecules were thus deposed on the Ru 55

Roberto González Gómez 194 NP in the presence of the same quantity of hydrides that result deprotonation of the carboxylic acids, as seen previously (figure 3.27). After structural optimization (see section 6.2.2), the mean adsorption energy of the carboxylate entities was obtained. for the pentanoic acid models and to -44.7 kcal.mol -1 for the octanoic acid systems (see section appendix B). The values of adsorption energies for pentanoic and octanoic acids are clearly reduced in comparison with that of ethanoic acid. Comparing the adsorption energies between pentanoic and octanoic acid, a slightly decrease is observed for octanoic acid vs pentanoic acid.

This may indicate a similar interaction strength for these two ligands.

CHAPTER III

Octanoic Acid-Capped RuNPs

Roberto González Gómez 195 Table 3.11, reports the E ads calculated for each studied system. There is no significant difference (< 2 kcal.mol -1 ) when the coverage value changed, at least between [10 -14] carboxylate moieties. Also, it can be observed that the longer the alkyl chain length, the lower is the adsorption energy of the carboxylic moiety onto Ru 55 NP. Interestingly, the adsorption energies of the pentanoic and octanoic acids are quite similar which can explain why no significant difference was observed by FTIR possibly as the result of a similar retrodonation phenomenon. The coordination of THF molecules at the surface of RuNPs synthesized with pentanoic acid and octanoic acid as stabilizers, as observed by FTIR analysis, may be due to the lower adsorption energies of these carboxylate moieties compared to that of ethanoic acid. The decrease in adsorption energy can cause instability of the NP surface. This may be the reason for THF to coordinate at the NP surface which compensates the stability of the metal surface.

The difference in adsorption energy observed with the length of the alkyl chain bearded by the carboxylic acids allows to explain the coordination of THF at the NP surface. But this result does not allow to explain why the π-backdonation is lower in the case of ethanoic acid compared to the two other ligands and also why a higher quantity of ethanoic acid is required to get stable RuNPs. One hypothesis is that the steric hindrance of the carboxylic ligands related to the alkyl chain also affects the formation of the nanoparticles and their stability.

To corroborate this assumption DFT calculations with dispersion effects were performed in the most crowded, Ru 55 (RCOO) 14 H 14 NP. The methodology was used in order to describe correctly the van der Waals interaction resulting form the ligand-ligand interactions, which can change the adsorption energy of the substrates onto the Ru 55 NP and explain the obtained data.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 196 The new computed DFT energies with the dispersion effects term were obtained by the empirical methodology developed by Grimme et al., [START_REF] Grimme | A consistent and accurate ab initio parametrization of density functional dispersion correction (dft-d) for the 94 elements H-Pu[END_REF] and corrected by the Becke-Jonson damping, [START_REF] Grimme | Effect of the damping function in dispersion corrected density functional theory[END_REF] the so-called the DFT-D3 method. The adsorption energies of the carboxylic moieties obtained by adding the dispersion effects is compared with its corresponding DFT-PBE adsorption energy (table 3.12). The average adsorption energies (DFT-D3) are slightly stronger than in calculations done without this correction (DFT), but it is shifted by an almost identical value, i.e. [7.3 to 8.5 kcal.mol -1 ]. Also, it does not change the relative adsorption energies, i.e. a lowering on going from ethanoic to octanoic moieties is still observed. Therefore, even considering the dispersion effects, it cannot be explained why the ligands with longer alkyl chain length have lower adsorption energies than the shorter ones, meanwhile they appear to be better stabilizing agents.

Also, owing to the similar adsorption energy obtained for the pentanoic and octanoic acids onto the Ru 55 NP model, the presence of free ligand in the (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs cannot be explained without taking into account the influence of THF even with the dispersion effects.

Therefore, more studies need to be performed in order to understand the role of THF.

THF Strength as Solvent-Controlled RuNPs

In the section 3.2.1, it was described the synthesis of RuNPs stabilized by 0.4 equiv. of octanoic acid in THF. The analysis provides a general panorama of the THF role and importance in the synthesis of this type of RuNPs. It is well-known that the organic solvent used for the synthesis Roberto González Gómez 197 of NPs plays a special role in the formation of nanosystems and even is utilized as control agent for the particle growth. Reports elucidate that the organic solvents can act as capping agents which bind onto the nanoparticles surface and limite its growth avoiding the metal agglomeration. [START_REF] Markus Niederberger | Metal Oxide Nanoparticles in Organic Solvents: Synthesis, Formation, Assembly and Application[END_REF] The ratio of ligand/solvent is crucial for controlling the size of the NPs and the relevance of this parameter depends on the solvent nature. [START_REF] Ramirez | Influence of organic ligands on the stabilization of palladium nanoparticles[END_REF] Previously it has been reported that the use of this type of solvents led to smaller nanoparticles, e.g. THF has been described for being used as controlled-growth agent for the synthesis of several MNPs, including RuNPs. [START_REF] Niederberger | Organic Reaction Pathways in the Nonaqueous Synthesis of Metal Oxide[END_REF] In the previous section it was described the synthesis of RuNPs in THF using 0.4 equiv. of octanoic acid as capping ligand. Characterization data evidenced the presence of free octanoic acid in the obtained powder of RuNPs even after their purification. Therefore, the objective is now to study the influence of a lower quantity of octanoic acid on the RuNPs formation while keeping the other parameters of the synthesis unfluctuating (3 bar H 2 ; r.t.; 15 h). Two [ligand]/[metal] ratios will be studied, namely 0.30 and 0.15 equiv.

After the chosen reaction time, the reaction was stopped by evacuation of the remaining hydrogen and the colloidal solution concentrated under high-vacuum before preparing grids for TEM analysis of the crude samples. This procedure is with the aim to see if the nanoparticles mean size can be reduced or if lower quantity of stabilizing agent can produce similar RuNPs.

The micrographs obtained for the RuNPs synthetized with 0.15 and 0.30 equiv. of octanoic acid in THF are presented in figures 3.28 a and 3.28 c, respectively. In both cases, RuNPs of similar morphology that are well-dispersed on the TEM grid can be observed. Both systems display a mean size around 1.5 nm. For both systems it can be observed small NPs that seems to be semi-homogeneous due to its large size dispersion that is slightly beyond of 50.0 % (standard deviation of 0.3 -0.4 nm).

Roberto González Gómez 198 Compared to previous observations when using 0.4 equiv. of octanoic acid, these new results show that the dispersion and morphology of the particles did not change when decreasing the [ligand]/[metal] ratio to 0.3 and 0.15 equiv. As a conclusion, it can be said that even with a low quantity of ligand the metal particles can be formed (0.15 equiv.) and that there is not a direct influence on the RuNPs size by adding the double amount of octanoic acid (0.30 equiv.). Probably, the only effect will be in the quantity of capping ligand surrounding the nanosystems as it was seen in section 3.1.6.

However, when a higher quantity of stabilizing agent (0.40 equiv.) is used for the synthesis of these RuNPs, a decrease in the NPs mean size was observed (ca. 0.15 nm), while the morphology was maintained. Since the standard deviation found for these systems is quite, a statistical treatment can be performed in order to show if the NPs mean size is really affected by the presence of higher amount of octanoic acid.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 199 The statistical treatment used was based on the Fisher test [START_REF] Raymond | An exact test for population differentiation[END_REF] and the bilateral Student's t-test, [START_REF] Ruxton | The unequal variance t -test is an underused alternative to Student's t -test and the Mann-Whitney U test[END_REF] the combination of these spectroscopic techniques allowed to have a clear information of the ligand effect on the mean size of the RuNPs.

𝐹 =

( Finally, in the [1580 -1500 cm -1 ] region (orange zone) the signal of the carboxylates is observed in the three nanosystems. As a conclusion, it was seen that the increase of the ligand in the synthesis of these RuNPs produced different type of moieties surrounding the nanosystem (free and coordinated (HA/A -)). Also, the lower the quantity of ligand, the cleaner the surface or more selective the ligand coordination will take place, going through the RuNPs stabilized by octanoates. For the first system (scheme 3.5 a) three molecules can be noticed (free ligand and octanoic acid coordinated in its protonated and deprotonated mode), meanwhile in the other system (scheme 3.5 b) only one moiety coming from the stabilizing agent was found (octanoate). This study provides a nice understanding of the coordination of the octanoic acid at the surface of RuNPs prepared in THF (solvent-assisted) depending on the amount of ligand introduced. It was observed that a [ligand]/[metal] ratio, as low as 0.15 equiv., is enough to have an efficient stabilization of small NPs of ca. 1.5 nm, even if the size distribution is quite large. This is attributed to the presence of THF, which was not observed in previous RuNPs stabilized with ethanoic or pentanoic acid. The THF presence was clearly observed onto the RuNPs surface as σ-THF or CO, which comes from its own degradation.

Increasing the ratio to 0.3 equiv. did not change significantly the mean size of the particles neither the broadness of the size histogram. But FTIR data provided a clear view of the difference between these two systems, namely the presence of only octanoates at the NP surface for 0.15 equiv. and the co-presence of octanoate and protonated acid both coordinated at the NP surface Roberto González Gómez 202 for 0.3 equiv. The nanosystem prepared with 0.4 equiv. led to smaller RuNPs (ca. 1.3 nm) with a surface interacting with both octanoates and protonated acids, and free ligand was also observed.

Therefore, the best system to take into account is (Ru x (C 7 H 15 COOH) 0.15 ) THF because it provides a cleaner surface with one type of interacting molecule (octanoate). Anyway, since the THF can be also considered as pollutant, the stabilization of RuNPs with octanoic acid will be performed as in previous cases with a non-coordinated solvent (pentane).

RuNPs Stabilized with Octanoic Acid in Pentane

MNPs have been widely synthetized by several methodologies, within which the organometallic approach was selected due to the well-defined homogeneous nanoparticles that can be obtained, leading as well to MNPs with a cleaner surface. [START_REF] Philippot | Organometallic approach to the synthesis and surface reactivity of noble metal nanoparticles[END_REF] Several ligands have been used

as stabilizing agents that led to different NPs size and morphologies, this offers the possibility to have a big range of metal NPs with various properties. [START_REF] Pan | Ligand-Stabilized Ruthenium Nanoparticles: Synthesis, Organization, and Dynamics[END_REF] The formation of this type of hybrid material (RuNPs and organic ligand) [START_REF] Viau | Ruthenium Nanoparticles: Size, Shape, and Self-Assemblies[END_REF] led to different applications due to its change in their characteristics and reactivity. [START_REF] Lara | Organometallic ruthenium nanoparticles: a comparative study of the influence of the stabilizer on their characteristics and reactivity[END_REF] In this study, it was shown that RuNPs can be synthetized by using linear alkyl carboxylic acids as stabilizing agents. Also, the formation of NPs even with small alkyl chain ligands (ethanoic acid) has been demonstrated, which is not often seen in the synthesis of MNPs. [START_REF] Pelzer | Organometallic Synthesis of Size-Controlled Polycrystalline Ruthenium Nanoparticles in the Presence of Alcohols[END_REF] Previously, it was also determined that the amount of stabilizing agent that will be needed to stabilize RuNPs depends on the alkyl chain length (see chapter II & section 3.1), effect that is magnified if a coordinated solvent it is used into the NPs synthesis (see and section 3.2.3).

In the section 3.2.3 was described that RuNPs can be synthetized by using 0.15 equiv. of octanoic acid in the presence of THF. Therefore, similar nanosystems will be attempted to form, but without coordinated solvents which will lead to cleaner NPs surface, as observed in previous systems synthetized with ethanoic and pentanoic acid.

In a first attempt, RuNPs were synthetized by following the organometallic approach in the presence of 0. It was evident that the RuNPs was not well-formed and probably only big metal pieces were produced or a mixture of different type of particles. Therefore, before any purification process and after elimination of the remaining hydrogen pressure, a drop of the concentrated crude solution was deposed on a c-flat holey carbon grid in order to perform a TEM analysis (see Thus, no well-defined ruthenium nanoparticles were synthetized by using only 0.10 equiv.

of octanoic acid in pentane (without THF). Displaying the real properties of solvent-assisted ligands like that the THF possess. Meaning that higher quantity of ligand needs to be added into the RuNPs synthesis if pentane is used as reaction media instead of THF.

Consequently, in order to get well-defined particles, an optimization of the quantity of octanoic acid was necessary to perform. This study is described in the following part.

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Octanoic Acid-Capped RuNPs Roberto González Gómez 204

Optimized Synthesis of RuNPs Stabilized with Octanoic Acid

To optimize the synthesis of the RuNPs, it was decided to add a double quantity of In these synthesis conditions, the initial pentane yellow solution changed to black very quickly (ca. 30 s) indicating the formation of RuNPs. The so-obtained colloidal solution appeared to be stable with no precipitate observed for more than two months. After 30 min under hydrogen pressure (splitted in 10 and 20 min of dynamic and static pressure, respectively), the reaction has been stopped by removing the gas phase under high-vacuum and the colloidal solution was concentrated for further electron microscopy analysis.

Since the obtained colloidal solution has shown to be stable for a long period of time, it can be assumed (due to previous empiric knowledge) that a high-stable RuNPs were synthetized, but to corroborate this assumption different studies needs to be done. For that purpose, a TEM grid was prepared by depositing a drop of the pentane crude and concentrated colloidal solution RuNPs synthetized with the same ligand but in THF (ca. 1.5 nm), again the influence of THF as solvent-assisted is noticed. Nevertheless, it is worth to point out the formation of the RuNPs with a low quantity of ligand (0.20 equiv.).

Since this system shows good stability and can be synthetized with a low quantity of ligand (avoiding solvent pollution), it can be taken as starting point to study the surface state of RuNPs In order to compare more precisely the three systems of RuNPs, the required ligand quantities for obtaining similar RuNP sizes in the same synthetic conditions are reported in table 3.13. Even if there is a slight deviation of the size measured comparing to a mean size of 1.5 nm, that is more pronounced in the case of octanoic acid, it appears that a lower quantity of carboxylic acid is required to get this mean size when the ligand has a longer alkyl chain length. In other words, using a carboxylic acid with a longer alkyl chain makes lower the required amount of ligand to stabilize the RuNPs. Therefore, it can be implied that the use of longer alkyl chain in the synthesis of RuNPs induces the formation of NPs with higher crystallinity and higher homogeneity than found for RuNPs stabilized with carboxylic acids which have shorter alkyl chain length. The WAXS analysis is consistent with the well-crystalline Ru hcp NPs determined by HRTEM, the estimated coherence length of ca. 2.2 nm is slightly overestimated from the mean size measured by TEM analysis. Such a difference has been previously observed by other authors in ruthenium [START_REF] Pan | Ligand-Stabilized Ruthenium Nanoparticles: Synthesis, Organization, and Dynamics[END_REF] and palladium [START_REF] Ramirez | Influence of organic ligands on the stabilization of palladium nanoparticles[END_REF] NPs.

Moreover, this last data is not in contradiction with TEM results since WAXS is a statistical technique which is highly sensitive to different size of synthetized objects. Therefore, these complementary studies provide a good notion on the mean size and crystalline structure of the As it can be seen from the vibrational spectrum (figure 3.34), there is no evidence of carboxylic acid asymmetric stretching vibration mode (R-COOH) in the [1800 -1600 cm -1 ] range.

Only one absorption band at ca. 1530 cm -1 is visible, same signal as observed for the (Ru x (C 7 H 15 COOH) 0.20 ) THF NPs. Thus, it can be said that this system behaves in a similar way than previous RuNPs systems stabilized with shorter alkyl chain carboxylic acids. In other words, the only signal that is observed in the [1800 -1500 cm -1 ] range (ν as R-COO zone) corresponds to the deprotonated carboxylic acid (octanoate) which is found at ca. 1530 cm -1 . Thus, the octanoic acid ligand followed the same deprotonation reaction when approaching to the metal surface, as for ethanoic and pentanoic acids. Roberto González Gómez 210

In the right part of the infrared spectrum, it can be identified three well-separated signals in the area [3000 -2850 cm -1 ] that can be attributed to the asymmetric (ν as ) and symmetric stretching (ν s ) vibration modes of the methyl and methylene groups of the carboxylic acid alkyl chain (CH 3 (CH 2 ) 6 COOH). It is important to note that no water is detected, as it was found in other systems stabilized with pentanoic or ethanoic acid. This can be explained from the decreasing of the ligand polarity and its affinity for water.

The vibration band observed at ca. 1530 cm -1 was assigned to the ν as vibration mode of the deprotonated octanoic acid interacting with the RuNPs (C 7 H 15 C=OO). The absence of any other signal in this region indicates the absence of free ligand or protonated ligand coordinated to the NPs (orange highlighted region; figure 3.34). At this point it can be said that there is no free carboxylic acid and that all the stabilizing agent present is surrounding the RuNPs as octanoate.

Other bands within [1500 and 1250 cm -1 ] could be identified for the asymmetric stretching mode (ν s ) of the carboxylic group (C 7 H 15 C=OO), and the C-H bending asymmetric (δ as ) and symmetric (δ s ) vibration modes of the alkyl chain (CH 3 (CH 2 ) 6 COO). In addition, a band attributed to the alkyl chain rocking mode (ρ(CH 2 ) n ) is visible at 720 cm -1 , meaning that there was no degradation of the ligand during the RuNPs synthetic procedure.

In the left part of the spectrum, two intense bands are present at ca. 1020 and 800 cm -1 that are assigned to coordinated THF. ([238], [START_REF] Bonnemann | The preparation, characterization and application of organosols of early transition metals[END_REF]) As previously mentioned for other carboxylic acid-stabilized RuNPs, the presence of THF can be explained by the washing process applied to purify the Ru x (C 7 H 15 COOH) 0.20 NPs. It is important to notice that no CO band is observed in the spectrum (blue highlighted region; figure 3.34), meaning that the THF degradation previously observed in other systems was not accomplished here.

In summary, FTIR spectroscopy provided good insights about the type of molecules surrounding the nanoparticles and contributed with general idea of the interaction occurred in the interface of this hybrid material. However, this technique is not sensitive enough to fully describe the type of molecules found at the RuNPs periphery. Therefore, to complete the Ru x (C 7 H 15 COOH) 0.20 NPs characterization, NMR techniques ( 1 H and 13 C) were utilized.

Contrary to other type of MNPs, which present some paramagnetic effects, ([259], [START_REF] Asensio | Knight Shift in 13C NMR Resonances Confirms the Coordination of N-Heterocyclic Carbene Ligands to Water-Soluble Palladium Nanoparticles[END_REF]) the RuNPs present only a small residual effect till no longer is considered as a NMR signal modifier and, even more, when there is an atom spacer between the recorded atoms affected for this CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 211 phenomenon and the metal surface. [START_REF] Tedsree | Formate as a surface probe for ruthenium nanoparticles in solution 13C NMR spectroscopy[END_REF] Therefore, it is possible to go deeper in the Ru x (C 7 H 15 COOH) 0.20 NPs surface characterization.

Previously, it was observed for (Ru x (C 7 H 15 COOH) 0.40 ) THF NPs, the presence of ligand excess and, in some point, the appearance of different type of molecules coordinated at the nanoparticle surface (protonated and deprotonated octanoic acid, THF, CO and sometimes PTHF). However, for other experiments performed with purified NPs (Pentane-THF cycles), less signals were observed.

Thus, it can be suggested that certain part of information could be lost once the particles are cleaned, due to the probable removal of weak bound organic molecules. As a consequence, the data could be biased. Therefore, in order to avoid this issue, the resonances experiments were performed form the fresh RuNPs colloidal solution.

1 H-NMR data were recorded from non-purified NPs. The crude colloidal suspension was just evaporated under high-vacuum and the residual powder dried under high-vacuum for 36 h.

Then the black powder containing the particles was re-dispersed into deuterated benzene (C 6 D 6 ), under inert atmosphere, just before performing 1 H-NMR experiments (see section 6.1.3.6). the presence of this type of peaks is usually used as a good proof of the ligand coordination at the NPs surface. ([163], [START_REF] Liu | Determination of monolayer-protected gold nanoparticle ligand-shell morphology using NMR[END_REF])

Thus, this broad peak can be assigned to carboxylic moieties interacting with the surface of the RuNPs. This assignation will be corroborated later on by complementary NMR techniques (vide infra). presence of coordinated THF and no other molecules was observed (CO, PTHF, free or coordinated protonated ligand). These data were corroborated by the 1 H-NMR spectrum where it was observed the absence of free ligand and THF, this last molecule was possible to be observed in the FTIR, because it was coming from the washing procedure. As a general conclusion, it can be said that the Ru x (C 7 H 15 COOH) 0.20 NPs are stabilized by octanoates and that all the ligand added is interacting with the metal surface (no excess).

The absence of free ligand was corroborated by both spectroscopies techniques, but the nonexistence of the protonated carboxylic entity coordinated onto the RuNPs was only proved by FTIR. Therefore, it is necessary to find another characterization technique that can validate this assumption. In previous experiment, it was reported the utility of use solid-NMR to verify the absence of free ligand and also the type of coordinating molecule onto the RuNPs surface.

This technique provides new information that was previously lost in the liquid state-NMR due to poor resolution of the spectrum induced by the low mobility of the ligands. The loss of motion generate an increase on the T 2 relaxation time and leads to broader signals that are difficult to interpret. ([179], [START_REF] University | Relaxation in NMR Spectroscopy[END_REF])

This phenomenon is magnified for atoms that are closer to the NP surface and even more those which are directly attached. [START_REF] Marbella | NMR Techniques for Noble Metal Nanoparticles[END_REF] Due to this phenomenon, it was not possible to identify any signals of the α-protons and carboxylic species from liquid state 1 H and [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-NMR data, respectively.

Solid-state NMR at the magic angle spinning (MAS) in high-speed condition is a powerful technique to circumvent problems of rigidity at NP surface and thus characterize deeper the interacting ligands. Hence, the obtained NMR spectrum show signals that were not possible to observe by solution NMR. In other words, it is possible to run [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C solid-state NMR to observe precise data on the carbon atoms which are closer to the NPs surface. [START_REF] Baquero | Highly Stable Water-Soluble Platinum Nanoparticles Stabilized by Hydrophilic N-Heterocyclic Carbenes[END_REF] The solid-state [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C CP Hahn-MAS NMR was recorded from purified Ru x (C 7 H 15 COOH) 0.20 NPs.

To avoid electric arching that appeared when using a powder of RuNPs as the result of the high metal content, it was necessary to dilute the particles into an inorganic support. For this purpose, the purified RuNPs were redispersed in THF solution, in concentrated condition. Then, the solution was deposed onto porous silica and dried by slow evaporation under inert conditions (see section 6.1.3.7).

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 214

The [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C CP Hahn-MAS NMR spectrum recorded for Ru x (C 7 H 15 COOH) 0.20 NPs diluted in silica is given on figure 3.36. It shows an intense peak close to 0 ppm corresponding to grease. Also, it presents two intense peaks at ca. 24.2 and 66.8 ppm that are assigned to the carbon atoms from THF as this solvent has been used for NPs deposition onto silica and can be present in the solid.

The first signal attributed to THF (ca. 24.2 ppm) is quite broad in comparison with the second one.

This can result from the presence of other signals in this region as it is expected for those of the methylene and methyl groups of the carboxylic molecules. In fact, on the right part of this signal, at lower ppm a small shoulder is observed that can be assigned to the methyl group of the carboxylic moieties (tail).

The signals marked with an "x" are assigned to molecules coming from the THF degradation. There is also a broad signal at ca. 192.1 ppm which can be attributed to the carboxylic carbon atom of the ligand when comparing with the same carbon of the free octanoic acid (ca. 180.4 ppm in CDCl 3 [START_REF] Bank | Octanoic Acid (C8 H16 O2)[END_REF] ). Previously, for the RuNPs stabilized with ethanoic and pentanoic acid, the peaks in solid [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C-NMR were observed to appear at lower field than those of the free ligand.

In particular, carboxylate molecules interacting with the RuNP surface presented left shifted signals. Here also, the peak observed at ca. 192.1 ppm and assigned to carboxylic carbon of the ligand interacting with the metal surface resonates at a lower field compared to that of free ligand (ca. 180.4 ppm in CDCl 3 [START_REF] Bank | Octanoic Acid (C8 H16 O2)[END_REF] ). The difference in chemical shift observed between the two peaks (≥ 10 ppm) associated to FTIR data presented before are in favor of the presence of octanoates at the RuNP surface and allows to exclude the existence of free octanoic acid and also of coordinated octanoic acids (protonated).

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 215 NMR studies lead to think that the three carboxylic acids used as ligands to stabilize RuNPs have a same fate at the NP surface. Once coordinated onto the ruthenium surface a deprotonation process takes place which makes them to interact with the ruthenium surface in carboxylate form.

Given the carboxylate form of the ligands, the carboxylic carbons suffer an electronic deprotection and their NMR signal is shifted to higher chemical shift (lower field).

The next comparison is performed in order to know the level of deprotection experienced by the carboxylates ligands when they are interacting with the RuNPs (table 3.14).

Roberto González Gómez 216 As it can be seen in the previous table, the value of the chemical shift of the carboxylate carbon increases with the length of the alkyl chain of the ligand. This type of correlation has been already observed and could be related to different variables as d-band center, ligand adsorption energies, NPs mean size, etc. [START_REF] Tedsree | 13C NMR guides rational design of nanocatalysts via chemisorption evaluation in liquid phase[END_REF] In this work, it was stablished that the signals found in the range of [186.0 -193.0 ppm] of the solid-state [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C CP Hahn-MAS NMR spectrum correspond to the carbon of the carboxylate molecule attached at the surface of the RuNPs. However, in previous works, it has been reported that for different types of MNPs, the carboxylic acids underwent a decarbonylation or decarboxylation reaction once they approach to the metal surface. ([265], [START_REF] Lamb | Reaction pathways for butanoic acid decarboxylation on the (111) surface of a Pd nanoparticle[END_REF]) As a consequence, it appeared necessary to corroborate if the signals observed in the region [186.0 -193.0 ppm] could correspond to CO or CO 2 molecules attached at the RuNPs surface as the result of a carboxylic acid degradation process.

For this purpose, a 2D solid-state NMR experiment has been performed. The 13 C Heteronuclear Correlation (HETCOR) MAS NMR program was chosen in order to define the atom correlation between the carbon and proton atoms of the ligands which lie on the RuNPs surface.

Thus, an HETCOR NMR spectrum has been recorded for Ru x (C 7 H 15 COOH) 0.20 NPs using the same probe as for [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C solid-state NMR, namely RuNPs dispersed into silica support (figure 3.37).

Roberto González Gómez 217 The diffusion-filtered 1 H-NMR spectrum shows that the broad peaks previously observed in the 1 H-NMR spectrum between [0.5 -2.7 ppm] corresponds to rigid molecules with low motion.

In fact, it can be seen how this broad signal remains as two broad peaks even when a high diffusion-filtration is applied.

The remaining peaks were attributed to the β -CH 2 (ca. It is important to notice than in this region there were some peaks or signal that were removed for the diffusion-filtration process. Since from other techniques, it was observed the absence of free ligand, a second type of interacting ligand can be proposed (weakly coordinated).

A possibility to try to corroborate this assumption is to consider the 1 H DOSY NMR data and analyze the evolution of the integration of the peaks in the [2.05 -0.85 ppm] area (that correspond to the methyl and methylene groups of the octanoates in interaction with the RuNPs surface), with the gradient strength. Thus, the diffusional attenuation was fitted to a Stejskal-CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 221 Tanner equation. This showed that it was not adequate to perform a mono-exponential analysis and indicated the probable presence of different types of interactions for the octanoates at the ruthenium surface. [START_REF] Nagashima | Stejskal -Tanner Equation Derived in Full[END_REF] Thus, the previous planted hypothesis of the presence of different type of coordinated ligands can be corroborated.

Then, the diffusional attenuation was fitted by a bi-exponential analysis which validated the presence of two different types of molecules interacting with the RuNPs surface. As a result, two different diffusion coefficients (D) were extracted. The first one with a value of D 1 = 1.7 x 10 -10 m 2 .s -1 which represents the 67.6 % of the signal weight and the second one, with a value D 2 = 6.4 x 10 -10 m 2 .s -1 , that possess 32.4 % of the measured signal weight. These two values are quite smaller than that extracted for free octanoic acid (monomer), namely D OcAc = 1.3 x 10 -9 m 2 .s -1 .

These results corroborate the absence of free ligand in solution as previously deduced from 1 H-NMR data. Concerning the two diffusion coefficients measured (D 1 and D 2 ) they reflect the behaviour of molecules with a different interaction strength at the RuNPs surface. The lowest diffusion coefficient (D 1 ) can be assigned to ligand molecules in strong interaction with the metal surface and the highest one (D 2 ) to ligand molecules with higher mobility that can be in fast exchange with free ligand in solution. Thus, it can be proposed that the ligand molecules are organized in different layers around the metal surface according to their interaction strength as represented in scheme 3.7.

Roberto González Gómez 222 It is important to remind that the detected species in solution can be either organic molecules or metal nanoparticles surrounded by ligands. Thus, the 3.8 nm hydrodynamic diameter can be compared to the mean size of the particles determined by TEM analysis (ca. 1.65 nm), that corresponds only to the metal core of the particles by removing the stabilizing ligand contribution.

Withdrawing two times the hydrodynamic diameter of the free ethanoic acid (also determined from its coefficient diffusion; 0.5 nm) from 3.8 nm leads to ca. 2.8 nm, a value which is quite higher than 1.65 nm obtained by TEM. This effect could be explained from a relaxation of the ligand attached at the RuNPs in the organic solvent [START_REF] Li | Two-Stage pH Response of Poly (4-vinylpyridine) Grafted Gold Nanoparticles[END_REF] and the temperature of the experiment. [START_REF] Mene | Influence of Water Temperature on the Hydrodynamic Diameter of Gold Nanoparticles from Laser Ablation[END_REF] Concerning the second type of interacting ligand, 1.0 nm hydrodynamic diameter, this value is not high enough to be assigned to another type of coordinated ligand and surprisingly it corresponds to the double of the hydrodynamic diameter of free octanoic acid monomer (0.5 nm).

Therefore, the previous assumption for being exchanging ligand can be validated.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 223 Finally, the DOSY analysis results (diffusion coefficients, D, and repartition in % of the corresponding species) can be taken as a huge advantage to define a mapping of the surface coverage of the NPs (see section 6.1.3.6.2). [START_REF] Coppel | Full Characterization of Colloidal Solutions of Long-Alkyl-Chain-Amine-Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State, Equilibria, and Affinity[END_REF] It is important to notice that this procedure is not easy to perform and that it requires to have a clean nanosystem, meaning that RuNPs with only the stabilizing agent attached at their surface are desired. The obtained results will provide the relative amount of strongly (D 1 ), weakly and exchanging ligand (D 2 ) interacting with the RuNPs surface.

Another important point is that the DOSY NMR experiments were carried out on non-purified nanoparticles. As a consequence, it is assumed that all the ligand introduced for the synthesis of the particles (0.20 equiv.) is still present in analyzed sample. The ligand species interacting with the RuNPs are of three types and noted as I s , I w and I f (see table 3.15). They correspond to strongly coordinated (I s ), weakly coordinated (I w ) and exchanging (I f ) ligands, respectively. The results show a high quantity of strongly coordinated ligand (67.6 %), a low quantity of weakly bonded ligand (18.7 %) and the lowest quantity of exchanging "free" ligand (13.7 %).

Then, given the RuNPs were not purified, these percentages have been converted into ligand quantities expressed in equiv. on the basis of the ligand amount introduced for the synthesis of the NPs (0.2 equiv.).

It is important to remark that the free ligand is the one which has no interaction at all with the metal surface. Meanwhile the exchanging "free" ligand is in continuous fast exchange with the weakly bonded ligand. showing that not all the surface atoms are occupied (in other words that the ruthenium surface is not totally covered by the stabilizing ligand) which leaves some place for other molecules like hydrides for instance. It is believed that these ligands are directly coordinated to the metal surface thus forming an inner shell of ligands around the NPs.

The other two type of interacting ligands have lower presence and can be considered to be present in an outer shell. [START_REF] Neouze | Surface Modification and Functionalization of Metal and Metal Oxide Nanoparticles by Organic Ligands[END_REF] Their estimated numbers were ca. 6.5 and 4.8 per RuNP for (l w ) (weakly coordinated) and l f , ("free" in exchange), respectively. The hypothesis is that the weakly coordinated ligands (l w ) are less grafted to the metal surface and thus they can be suitable for exchanging with the third type of ligands l f . It is worth to point out that these ligands which forms the outer shell are in constant fast exchange, namely in equilibrium. A better view of the findings can be observed in the scheme 3.8.

Roberto González Gómez 225 The presence of a weakly bonded ligand which is in constant exchange with labile stabilizing agent, it is sometime difficult to understand because it can be confused with the real free ligand (no interaction with the metal surface). Thus, in order to complete these results and try to better understand the difference between l w /l f ligands and totally free ligands in solution, a Nuclear Overhauser Effect (NOESY) NMR experiment was performed from the same deuterated benzene solution as for previous DOSY NMR experiment (see section 6.1.3.6.3).

The signals of the NOESY spectrum (figure 3.40) can be correlated with the molecular weight of the corresponding solubilized species. [START_REF] Post | Exchange-transferred NOE spectroscopy and bound ligand structure determination[END_REF] It is admitted that a positive NOE signal corresponds to small molecules which are not interacting with the NP surface (free in solution). [START_REF] Williamson | Chapter 3 -Applications of the NOE in Molecular Biology[END_REF] The NOESY spectrum recorded for the Ru x (C 7 H 15 COOH) 0.20 NPs shows only positive NOE (blue shapes) for the signal in the region [3.5 -5.0 ppm] that belong to an impurity which is free and no interacting with the metal surface.

However, there is no positive NOE in the region [0.5 -2.7 ppm], that corresponds to the area where the peaks of free octanoic acid are expected to appear (figure 3.40 blue signals).

Roberto González Gómez 226

Therefore, this result corroborates that there is no free ligand in the colloidal solution and that the weakly bonded ligands (l w ) are actually in fast exchange with so-called "free" exchanging carboxylates. The oxygen cannot be quantified by this analysis but considering that the whole carbon source is the octanoic acid added for the RuNPs synthesis, is possible to calculate the weight percentage of oxygen (6.8 %), meaning than 69.6 % of the sample weight is metal and 30.4 % comes from an organic source. This data can be converted to molar equivalents leading to a result of 0.31 molar equivalents of octanoic acid into the sample.

This result is slightly higher than the expected for the organic phase (0.2 equiv.), which means that the octanoic acid is not the only carbon source. This is not surprising because the elemental analysis was performed after washing the RuNPs by several cycles of pentane-THF and previously the presence of coordinated THF (FTIR) was observed. Therefore, it can be implied that the THF is present into the purified sample and affect the elemental analysis measurements.

The Ru x (C 7 H 15 COOH) 0.20 NPs metal content can be obtained by (ICP-AES). [START_REF] Olesik | Elemental analysis using ICP-OES and ICP/MS[END_REF] The analysis was performed for the purified RuNPs in the same way that the elemental analysis (see section 6.1.3.2) was done. The results are presented in the table 3.18. Roberto González Gómez 228

The ICP results indicate that the particles contain 62.2 wt% of ruthenium, which leads to 37.8 wt% of organics. The result can also be transformed to molar equivalents, which indicates that if all the organic source comes from octanoic acid, it should be around 0.43 equiv. of it, being this the double of the added ligand into the NPs synthesis. However, the presence of another organic molecules attached at the NPs surface, once the purification process is performed (THF), is known. Still, the obtained result indicates a notable yield of RuNPs into the analyzed sample. [START_REF] Baquero | Highly Stable Water-Soluble Platinum Nanoparticles Stabilized by Hydrophilic N-Heterocyclic Carbenes[END_REF]

Quantification of Reactive Hydrogen at the Surface of Ru x (C 7 H 15 COOH) 0.20 NPs

The number of octanoates ligands that surround the RuNPs has been estimated through NMR analyses. But given the synthesis conditions applied to produce the particles, hydrogen atoms are expected to be coordinated at the RuNPs surface.

From previous published work, it has been seen than these hydrides are highly reactive. [START_REF] Philippot | Organometallic Ruthenium Nanoparticles and Catalysis[END_REF] Therefore, it is possible to titrate the reactive hydrogen that lies on the RuNPs surface by exposing the Ru x (C 7 H 15 COOH) 0.20 NPs to 2-norbornene, as previously described for the RuNPs stabilized by ethanoic acid. For this methodology, the RuNPs were used as a reductive catalyst for the olefin, the procedure was performed at r.t. with no extra hydrogen added (see section 6.1.4.1). The alkene conversion was low but sufficient to be detected by GC analysis (see section 6.1.3.4).

The reaction performance is an indirect way to quantify the number of reactive hydrogens at r.t., because the olefin can only be reduced by the hydrogen present at the RuNPs surface (scheme 3.9). Thus, the GC obtained data allowed to calculate the hydrogen surface coverage on In the next section, theoretical tools will be used in order to apprehend the surface composition of the Ru x (C 7 H 15 COOH) 0.20 NPs.

Titration of Ru x (C 7 H 15 COOH) 0.20 NPs by DFT calculations

A combination of theoretical and experimental characterization has been proven to be an efficient approach for get a relevant map of the surface of RuNPs stabilized with carboxylic acids (see chapters II and section 3.1 Thus, on the surface of the Ru 55 NP model different co-adsorbed quantities of octanoates and hydrogen were set up, as previously performed with other NPs systems . The structures were then optimized and the DFT energies were obtained (see section 6.2.2). We shall again recall that DFT energies are calculated for a 0 K, 0 Pa system in vacuum, and that the aim of the ab initio thermodynamics method is to introduce thermodynamic variables (T, p) for the same system in equilibrium with a reservoir of stabilizing species. This strengthens with the comparison with experimental findings and it is expected to shed light on the actual surface state of the metal NP.

The ab initio thermodynamics program has a database of standard enthalpies and entropies of ligands, in gas phase or in a solvent, gives the possibility to obtain Gibbs free energies in a suitable format for surface plotting softwares. This graphical representation highlights which is the most stable optimized structure when the adsorbed ligands are in equilibrium at certain thermodynamic conditions (T, p).

Owing to previous theoretical analysis here reported and the experimental findings for this nanosytem, it can be infered than the Ru x (C 7 H 15 COOH) 0.20 NPs will have a relatively high amount of octanoate and a low amount of hydrides, i.e. significantly lower than 1.3 H/Ru surf . [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Therefore, it is not necessary to study structures with possess a lot of hydrides and a low quantity of stabilizing agent, because they will not be stable at least in the synthetic thermodynamic conditions.

The selected structures that have been considered are presented in figure 3.41. The information obtained from these built nanostructures will be taken as a basis for corroborating the information found experimentally during the ligand coverage titration.

Roberto González Gómez 232 Roberto González Gómez 233 The Gibbs free energies (Δ a G°) were obtained for these eight optimized structures by setting the temperature at 300 K. This was possible by using the ab initio thermodynamics methodology where the ligand-metal vibration corrections were accounted for (see section 6.2.7

and appendix D). As already done in the pentanoic acid case, the metal-COO corrections were transferred from the ethanoic acid case. This approximation can safely be used because the most important vibrational corrections are originated from H-metal vibrations and not from the carboxylic moiety.

The Gibbs free energies calculations were obtaining by using the chemical potentials of octanoic acids solvated in THF (see section 6. Roberto González Gómez 234 ).

The phase diagram shows that only one of the optimized structures ( 71) is not stable in any range of the displayed graphic. In the diagram, it can be seen that the most stables structures have low quantity of hydrides together with a high quantity of octanoates.

The low and high concentration and pressure domains considered in the phase diagram are displayed only to give reference data, although they do not correspond to the actual experimental synthesis conditions. Regarding the experimental octanoic acid concentration, we considered the amount of ligand introduced for the NPs synthesis. It can be considered as quite accurate due to the data obtained by DOSY analysis, that reveal an absence of free octanoic acid and that all the added ligand interacts with the NPs surface. Meanwhile, similar calculations were performed for the hydrogen pressure taken into account the remaining reductive entities after the RuNPs synthesis (hydrogen titration).

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 235

The obtained results indicate that at the equilibrium there is a concentration of octanoic acid of ca. 10 -3.0 mol.L -1 , while for the hydrogen pressure is ca. The DFT titration results can be compared with the experimental ones obtained by DOSY NMR analysis and hydrides titration, where it was observed similar behavior (low quantity of hydrides and high amount of octanoates). As can be seen in table 3.20, both techniques are in very good agreement providing close values. This combined approach gives as an outcome a nice accurate and precise surface mapping of this Ru x (C 7 H 15 COOH) 0.20 NPs. In other words, the combination of the experimental and theoretical characterization gives the possibility to have an overall picture of this hybrid material that is not easy to characterize due to its size and to several more issues, such as the titration of such low-concentration surface species by DOSY-NMR.

Theoretical [0.2 -0.3] [0.3 -0.6]
Owing the results obtained by the theoretical titration and its reliability, some trends can be evaluated. For example, it was observed that RuNPs can be synthesized by using diverse carboxylic acids which have different alkyl chain length. But curiously, it was detected that the shorter the alkyl chain length of the ligand the higher was the quantity of stabilizers needed to form similar size of RuNPs. In order to corroborate this trend, a parallel can be performed with the results obtained by the DFT titration (table 3.21).

CHAPTER III

Octanoic Acid-Capped RuNPs

Roberto González Gómez 237 This comparison highlights the high agreement achieved by applying in parallel experimental and theoretical titrations of the RuNPs stabilized by carboxylic acids bearing different alkyl chain lengths. From these data it can be proposed that the longer the alkyl chain length of the ligand, the lesser the quantity of stabilizing agent needed to stabilize the nanosystem. This can be explained by a steric hindrance effect of the alkyl chain of the ligand that is expected to increase with its length increase, that can reinforce the stabilization effect of the ligand. Roberto González Gómez 239 The increase of the sharper signals is a direct proof of the escalation of the organic molecules mobility in the solution. However, at this stage of the study these molecules can be either free in solution, or weakly interacting (I w ) with the RuNP surface or in fast exchange (I f ). The only possible conclusion is that there is more ligand that can be exchanged or that can be free in

Surface Saturation of Ru x (C

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 240 the solution. 2D DOSY NMR experiments were then carried out for each step of the addition of free octanoic acid in order to estimate the quantities of ligands depending on their nature (l s , l w , l f ).

From the 1 H DOSY NMR results (table 3.22) it can be observed that the quantity of strongly coordinated ligands (l s ) did not vary so much and remained in the range [20.7 -25.0 L/Ru NP ] despite the increasing addition of free octanoic acid in the NMR tube (see section 6.1.3.6.2). This observation leads to the conclusion that no other octanoate got coordinated at the surface of the Ru x (C 7 H 15 COOH) 0.20 NPs probably because their surface was already saturated or due to their steric hindrance. It can also be inferred that no coordinated ligands were released from the surface of the particles and that the strongly coordinated ligands form a strongly protective ligand shell. [START_REF] Desireddy | Ultrastable silver nanoparticles[END_REF] This assumption is not in contradiction of the possible coordination of other small moieties like THF due to its size in comparison with the carboxylates (coordination in bridging mode forming a five ring metallacycle).

The DOSY calculations need to be taken carefully due to the error presented in DOSY NMR measurements which is at minimum 8.0 % and can increase depending on the experimental variable and the type of equipment used for the study. [START_REF] Thrippleton | A fast method for the measurement of diffusion coefficients: One-dimensional DOSY[END_REF] equiv. has been considered as the surface saturation point of these Ru x (C 7 H 15 COOH) 0.20 NPs. Also, it was observed that the addition of extra ligand does not affect the inner shell (I s ) of this system (no release or incorporation of ligand). In addition, the quantity of weakly coordinated ligand (I w ) is maintained after 0.10 equiv. of ligand is added meanwhile the amount of free exchanging ligand increases (I f ).

NMR results indicate that there was no significant variation of the number of octanoate ligands in the inner (l s ) and outer (l w ) ligand shells, one can wonder on a hydrodynamic size compression or expansion depending on the quantity of extra ligand added. ([277], [START_REF] Tsai | Hydrodynamic Fractionation of Finite Size Gold Nanoparticle Clusters[END_REF]) With the objective to find an answer to this question, it is reported in table 3.23 the hydrodynamic diameters of the different l s and l w ligands for each amount of octanoic acid added in the NMR tube.

CHAPTER III

Octanoic Acid-Capped RuNPs Roberto González Gómez 242

The calculation of the hydrodynamic diameter of the strongly coordinated ligands will determine if the main entity of the hybrid material (inner shell) stand or it is modified. Also, it is plausible to observe the ligand addition influence in the outer shell, which should be decreased with each addition approaching to the hydrodynamic size of the free octanoic acid monomer (0.5 nm).

It can be seen that the hydrodynamic diameter of the strongly coordinated ligands (I s )

remains almost the same (size range 3.8-4.1 nm) even at high quantity of octanoic acid added. On the other hand, the values calculated for weakly bonded and exchanging ligands (l w ) show a decrease of the hydrodynamic size from ca. [1.0 to 0.7 nm]. This can be due to an increase of the "free" fast exchanging ligand in comparison with the octanoic moieties weakly coordinated. To remember that the I w ligands is the average of weakly bonded octanoates and the "free" exchanging ligands. The evidence reported from the DOSY analyses are not enough to determine if there is a compression or extension of the inner shell of the nanoparticles, due to the error presented in the measurements. Therefore, to know more about the metal component behavior, a TEM analysis was performed for the Ru x (C 7 H 15 COOH) 0.20 NPs once + 100 % of ligand was added. Meaning that the analysis was performed after the last NMR experiment which has 0.40 equiv. of octanoic acid into the dissolved RuNPs.

The microscopy analysis was obtained from the deposition of a single drop of the deuterated solution onto a holey carbon-covered copper grid (see section 6.1. Even with all these studies, it is difficult to identify the difference between free octanoic acid and "free" fast exchanging ligand (I f ). Therefore, NOESY NMR data were also recorded for each ligand addition right after the DOSY analysis. It is important to remind that a positive NOE indicates an organic moiety that is completely free which has no interaction with the RuNP surface (see section 6.1.3. From these results, it can be concluded that after addition of 0.2 equiv. of octanoic acid a part of it is clearly free and does not exchange with ligands interacting at the metal surface.

These extra octanoic acid molecules seem to be totally free in the solution.

Exposure of Ru x (C 7 H 15 COOH) 0.20 NPs under 13 CO Atmosphere

It is well-known in the field of MNPs that establishing the location of the capping ligands is highly helpful to understand better the catalytic reactivity at the MNPs surface. [START_REF] Abbott | CO Adsorption on Monometallic and Bimetallic Au -Pd Nanoparticles Supported on Oxide Thin Films[END_REF] Thus, in order to complete the surface mapping of the Ru x (C 7 H 15 COOH) 0.20 NPs, it is worthy to know which sites of the metal surface are available to host extra molecules (like ligands, hydrides or CO) or perform catalysis. [START_REF] Vindigni | Catalytically active gold sites: nanoparticles, borderline sites, clusters, cations, anions? FTIR spectra analysis of 12 CO and of 12 CO-13 CO isotopic mixtures[END_REF] CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 245

Solid state-NMR spectroscopy is a powerful tool to get information not only concerning the ligand atoms that are close to the MNPs surface, as it was described before, but also to evaluate the presence of potential active sites at the MNP surface. For that purpose, CO can be used as a probe molecule by reacting it with preformed RuNPs. By this way, trustworthy information can be reached about the available sites for catalysis in different nanosystems.

Previous published works dictates that the coordination of CO at RuNPs surface can take place in terminal, bridging or multicarbonyl modes. The knowledge on the existing coordination modes can be correlated to the nature of active sites present at the NP surface. In general, terminal CO are found to coordinate onto apexes or edges of the NPs, meanwhile bridging CO is coordinates onto the NP faces (figure 3.47). [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Figure 3.47 Coordination modes of CO at the NPs surface in relation with the free surface sites. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] Apart from the information on the coordination sites of CO at metal surface, information on its mobility onto the NP surface can also be obtained. For example, RuNPs stabilized with polyvinylpyrrolidone (PVP) have been reported to present only bridging COs at low concentration of CO but also terminal COs at higher concentration. Meanwhile RuNPs stabilized by bis(diphenylphosphino)butane (dppb) showed an intense signal for terminal COs together with a broad signal of bridging CO. This derives from a lower quantity of free surface sites for the CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 246 dppb-stabilized RuNPs due a high surface coverage by the bulky diphosphine ligands. As a consequence, some RuNPs can be more appropriate compared to others for a given selective catalysis depending on the quantity and nature of their free surface which may depend strongly on the stabilizing agent used. [START_REF] Novio | Surface chemistry on small ruthenium nanoparticles: evidence for site selective reactions and influence of ligands[END_REF] Carbon monoxide was reacted with a sample of Ru x (C 7 H 15 COOH) 0.20 NPs dispersed into porous silica inside a Fisher-Porter (1 bar of 13 CO; see section 6.1.3.7). After 24 h under vigorous stirring followed by evacuation of the rest of CO gas under high-vacuum, the preparation of the NMR rotor was performed under inert atmosphere in a glove-box (see section 6.1.4.2).

As a blank test, porous silica was impregnated with a THF solution of octanoic acid, then dried by slow evaporation and finally exposed to 1 bar of [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] Thus, due to the octanoate coordination mode, it should be unlikely to be coordinated onto apexes and edges and consequently should happen only onto faces. This seems to be supported by the observation of COs deposition only on the edges and apex or the RuNPs surface.

In hydrides which are similar (ca. 0.2 of octanoate and hydride per Ru surf ). It was described that there are strongly coordinated ligands and others which are weakly coordinated or in exchange. Also, it was shown that the stabilizing effect offered by the octanoates is very high and that the formed RuNPs do not evolve even in the presence of extra ligand (up to 0.2 equiv. of added octanoic acid).

Finally, CO can coordinate only onto apexes and edges. The next step is to apprehend the catalytic reactivity of these RuNPs. This will be presented in the next section on the basis of DFTcalculations regarding the HER reaction.

Evaluation of Ru x (C 7 H 15 COOH) 0.20 NPs for the HER by DFT Calculations

In this work, a deep view of the relationship between the metal ruthenium NP core and the carboxylic acid ligands for stable hybrid materials (RuNPs) has been reported. Given the quantity of ligand needed to stabilize similar mean size of RuNPs, we can assume that the longer the alkyl chain length of the studied ligands, the better the stabilization of the system.

According to this, it could be assumed that the adsorption energy for the longer alkyl chain ligands should be superior than shorter stabilizing agents, but the DFT results shows the opposite (see section 3.2.2). It means that that other variables or principles have a bigger role in the metal nanoparticles stabilization.

From a general point of view, it is known that the stabilization of these nanosystems relies on the ligand coverage, on adsorption energies and on steric hindrance. [START_REF] Walter | A unified view of ligand-protected gold clusters as superatom complexes[END_REF] It has also been suggested by some authors that a higher amount of ligands produce more stable nanoparticles. [START_REF] Neouze | Surface Modification and Functionalization of Metal and Metal Oxide Nanoparticles by Organic Ligands[END_REF] In this work, this property was observed by changing the synthesis L/[Ru] ratio. Taking into account the obtained data about the RuNPs stabilization with linear carboxylic acids, it can be inferred that the steric hindrance of the organic moieties which interacts with the RuNPs surface produce a protective barrier that makes them more stable, making highly important this variable. ([205], [START_REF] Aikens | Electronic Structure of Ligand-Passivated Gold and Silver Nanoclusters[END_REF])

Metal nanoparticles possess a high affinity for hydrogen, and RuNPs is well-known to be remarkable in this area. As well, these nanosystems are well-known for their catalytic performance CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 249 in various reduction reactions. ([59], [START_REF] Zhao | Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties[END_REF]) In such reactions, the relationship between the adsorption and desorption of hydrogen (or any moiety) onto the RuNPs surface becomes crucial and will determine the nanosystems catalytic performance. [START_REF] Kanninen | Influence of ligand structure on the stability and oxidation of copper nanoparticles[END_REF] Thus, the previous reported studies about the surface mapping of the RuNPs and especially the recognition of the metal surface free sites becomes a variable of high interest.

Knowing these data could offer the advantage of performing selective chemistry based on metal nanoparticles surface studies. [START_REF] Novio | Surface chemistry on small ruthenium nanoparticles: evidence for site selective reactions and influence of ligands[END_REF] The theoretical evaluation of Ru x (CH 3 COOH) 0.40 and Ru x (C 4 H 9 COOH) 0.30 NPs in the hydrogen evolution reaction (HER) has been described in previous sections, by following the NØrskov fundamental work. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] In NØrskov published methodology, the H adsorption Gibbs free energy (ΔG H ) is related to the exchange current in the HER reaction, the best catalysts such as platinum electrodes being characterized by ΔG H close to be zero. Therefore, the assessment of this reaction can be performed by calculating the hydrogen adsorption Gibbs free energy (ΔG H ) on the most stable Ru 55 NP structure found by DFT titration, Ru 55 (C 7 H 15 COO) 14 (H) 14 , focusing specially in the free sites observed by CO deposition (edges and apexes). In order to save computational time, it was followed the usual strategy which consists in evaluating ΔG H by an empirical addition of 5.5

kcal.mol -1 to ΔE H (see section 6.2.11).

However, in order to have a complete view of the surface properties of this system and to compare them with the previous calculations done on the ethanoate-and pentanoate-stabilized It is interesting to notice that the favorable sites which have a good relationship between the adsorption and desorption of hydrogen are also the free sites found by CO RuNPs deposition (apexes and edges), previously described.

From these results, it can be concluded that the Ru

Conclusion

In previous sections, RuNPs were synthetized in pentane by using carboxylic acids with different alkyl chain length (ethanoic and pentanoic acid), both were characterized by experimental and theoretical approaches. Consequently, some trends about the ligand stabilization and the surface composition (better stabilization and lower surface coverage for NPs stabilized with pentanoic acid) were observed. The role of THF as cleaning agent was observed by its deposition and degradation onto the RuNPs surface.

Thus, in order to study the influence of an even longer alkyl chain compared to the system prepared with ethanoic and pentanoic acid previously described, RuNPs were synthetized by using octanoic acid. The study, characterization and its corresponding comparison with RuNPs previous synthetized was described in the second part of this chapter.

Firstly, RuNPs were synthetized by adding the same amount of octanoic acid (0.40 equiv.), as previously performed for other nanosystems but in THF, solvent-assisted. As a result, highly-stable RuNPs, presenting an excess of ligand and different type of coordinated molecules (protonates and deprotonated octanoic acid), were found. Due to its high stabilization, DFT studies about their adsorption energy onto the Ru 55 NP model were completed. The results were not favorable because they show lower adsorption strength even when dispersion effects were added.

However, a trend was observed: longer the alkyl chain length of the adsorbed molecule (linear carboxylate), the lower its adsorption energy on the Ru 55 NP surface. Meaning that probably another factors are involved in the RuNPs stabilization, like the solvent or the ligand barrier.

Considering the previous result and to determine the real role of THF, different RuNPs were synthetized by decreasing the amount of stabilizing agent (0.30 & 0.15 equiv.), observing that even when a low quantity of ligand (0.15 equiv.) is used to the synthesize the nanosystems, it was possible to stabilize RuNPs with a nice morphology and a small mean size. Also, an absence of extra ligand and coordinated octanoic acid was observed. The only molecule that interact was the octanoate, but still it can be observed some THF pollution at the surface of the RuNPs.

In order to eliminate this intermediate and see the real effect of the alkyl chain length, the RuNPs were synthetized with a fewer amount of octanoic acid (0.1 equiv.), without the presence Roberto González Gómez 253 of THF, in pentane. The results were not promising, since it leads to a mixture of different nano and microstructures. Thus, the role of THF and its importance was completely described. Next, the RuNPs were synthetized with a higher quantity of ligand (0.2 equiv.) and as a result, the formation of very nice NPs, which seems to be homogeneous, well-dispersed and with a mean size of ca. 1.65 nm, being quite like previous optimized RuNPs stabilized by ethanoic and pentanoic acid (ca. 1.5 nm), was observed. The quantity of stabilizing agent used for the synthesis of this RuNPs was lower than the one needed for other systems (0.40 and 0.30 for ethanoic and pentanoic acid, respectively), which shows a direct trend about the influence of the alkyl chain length. It was observed that longer the alkyl chain length of the ligand, lower will be the quantity of ligand needed to form similar mean size of RuNPs ([1.5 -1.7 nm]). This information, in addition to the previous one obtained for the ligand adsorption energy, indicates that the steric hindrance of the stabilizing agent has a big effect on the RuNPs formation.

Thus, the addition of 0.20 equiv. of octanoic acid for the RuNPs synthesis in pentane was taken as the optimal L/[Ru] ratio for the formation of a homogeneous well-dispersed nanosystem, that can be comparable with other systems, without THF pollution. Therefore, the introduced. In this case, the presence of free ligand was finally observed.

In order to complete the surface mapping of this system, [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] CO was deposed onto the nanosystem. Then, it was observed that the surface of the nanoparticle was crowded, and the deposition of this marked gas only can be performed in the apexes and edges of the Ru x (C 7 H 15 COOH) 0.20 NPs. Meaning that the available sites for catalysis in this nanosystem are in the apexes and edges.

Finally, in order to evaluate its possible catalytic activity, an evaluation of the hydrogen adsorption and desorption on the optimal RuNPs found by DFT calculations (Ru 55 (C 7 H 15 COO) 14 (H) 14 ) was performed. It was observed that this parameter was too high in the planes and quite good at the apexes and edges, which was a quite good result owing the data obtained by [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] ). Thus, it can be said that even when the use of octanoic acid produce a more stable system with lower surface coverage, it is not necessarily the best catalyst. In other words, a suitable catalyst for HER reaction will be the RuNPs which possesses middle surface coverage and middle alkyl chain length, namely RuNPs stabilized by pentanoic acid, Ru x (C 4 H 9 COOH) 0.30 .

Due to the hydrogenation catalytic properties of the RuNPs, it is possible that the synthesis of RuNPs with aryl carboxylic ligands will produce a reduction of the ligand. Therefore, in order to circumvent this issue a ligand exchange was proposed as strategy aiming to introduce aryl ligands onto the RuNPs surface. This study will be presented in the next chapter.

Introduction

Roberto González Gómez 259

Introduction

MNPs have demonstrated to be a promising material for catalysis because they combine the advantages present in both, homogeneous and heterogenous catalysis. Their driving force relies on their properties, which lies between bulk materials and molecular compounds. For example, MNPs present catalyst recycling, product separation, catalytic mild reaction conditions, etc. [START_REF] Astruc | Nanoparticles as recyclable catalysts: the frontier between homogeneous and heterogeneous cata lysis[END_REF] In fact, the interest in these materials is increasing in both academia and industry domains, mainly due to their higher active surface area that can be tuned to improve their stability, viability and selectivity. [START_REF] Fedlheim | Metal nanoparticles: synthesis, characterization and applications[END_REF] The reactivity of MNPs was reported to be strongly linked to their synthesis methodology, i.e., variety of the supports, reaction solvent, nature of the metal source, etc., since all these parameters will lead to different sizes, morphologies and structures. [START_REF] Okitsu | Catalytic Applications of Noble Metal Nanoparticles Produced by Sonochemical Reduction of Noble Metal Ions[END_REF] Also, it has been determined that the viability and functionality of MNPs, in a specific catalytic reaction, can be modified by exchanging the surrounding molecules that interact with the metal surface as a ligand barrier. [START_REF] Woehrle | Thiol-functionalized, 1.5-nm gold nanoparticles through ligand exchange reactions: Scope and mechanism of ligand exchange[END_REF] Moreover, these nanomaterials can act as catalysts for several reduction reactions, especially for the arenes hydrogenation, ([286], [START_REF] Alsalahi | Green Synthesis of Rhodium Nanoparticles that are Catalytically Active in Benzene Hydrogenation and 1-Hexene Hydroformylation[END_REF]) which cannot be obtained in normal conditions (figure 4.1). [START_REF] Schoenmaker-Stolk | The catalytic hydrogenation of benzene over supported metal catalysts: I. Gas-phase hydrogenation of benzene over ruthenium-on-silica[END_REF] Several published reports have shown the potentiality of RuNPs to perform partial [START_REF] Silveira | The Partial Hydrogenation of Benzene to Cyclohexene by Nanoscale Ruthenium Catalysts in Imidazolium Ionic Liquids[END_REF] or total hydrogenation of arenes. ([289], [START_REF] Hydrogenation | Ru nanoparticles immobilized on montmorillonite by ionic liquids: a highly efficient heterogeneous catalyst for the hydrogenation of benzene[END_REF]) Therefore, these nanosystems are suitable for being intensively investigated in order to increase their selectivity in several hydrogenation reactions, such as aromatic compounds reductions and their derivatives. [START_REF] Cui | Highly selective hydrogenation of arenes using nanostructured ruthenium catalysts modified with a carbon-nitrogen matrix[END_REF] Introduction Roberto González Gómez 260 The RuNPs presented in this dissertation were synthetized by following the organometallic approach using hydrogen as reactive gas to decompose the metal precursor and reduce the olefinic ligands into alkanes (see section 1.2.3). It has been shown that the formed RuNPs bear hydrides at their surface coming from the synthesis conditions and also from the deprotonation of the carboxylic acid ligands.

Owing to the well-known catalytic properties of RuNPs towards the hydrogenation of insaturated molecules and most particularly of aromatic systems, partial or total reduction of aryl groups can be expected when they are present in the skeleton of the stabilizing agents used for the synthesis of the RuNPs (figure 4.

2).

This side-reaction has been already observed in RuNPs stabilized by arylphosphines for instance [START_REF] García-Antón | Reactions of olefins with ruthenium hydride nanoparticles: NMR characterization, hydride titration, and room-temperature[END_REF] but not for RuNPs synthesized in the presence of 4-(3-phenylpropyl)pyridine. ([104], [START_REF]Diphosphite ligands derived from carbohydrates as stabilizers for ruthenium nanoparticles: promising catalytic systems in arene hydrogenation[END_REF])

This difference may result from the coordination of the two aromatic parts of Thus, the direct synthesis of RuNPs by using as stabilizer a photosensitive ruthenium complex containing aromatic groups like the ruthenium trisbipyridine complex ([Ru(bpy 3 )] 2+ ) envisaged to get hybrid nanomaterials can be problematic, due to the pyridine moieties possible reduction that would change the optical properties of the ruthenium complex and consequently of the hybrid material.

In order to avoid such difficulties, an alternative strategy has been envisaged to perform the anchoring of bipyridine containing ruthenium complexes with pending carboxylic acid groups at the surface of RuNPs, namely a ligand exchange reaction.

In this chapter, studies on ligand exchange between preformed RuNPs stabilized by octanoic acid and added benzoic acid or trifluoracetic acid will be presented. Benzoic acid was selected because it contains an aryl group, thus mimicking the PS complex, and also due to its different acidic properties compared to alkyl carboxylic acids. Trifluoroacetic acid was chosen in order to study the ligand exchange reaction using an even more acidic ligand. The obtained results will be presented in the next parts of this chapter.

. Roberto González Gómez 262

Ligand Exchange at RuNPs Surface: Octanoic Acid vs

Benzoic Acid

As previously described, the ligand exchange between performed RuNPs and aryl ligands was the chosen methodology to introduce ligands which possess aromatic behavior onto hydrogen catalytic reactive NPs. In this case, the selected moiety to be studied was the simplest aromatic carboxylic acid, the benzoic acid. This molecule will be used as prove of content to further ligand exchange with the actual photosensitizer that has carboxylic acid as anchoring groups.

In the precedent chapters, theoretical calculations have shown that among the different samples of carboxylic acid-stabilized RuNPs prepared, apparently the most reactive ones for HER should be those prepared with 0.3 equiv. of pentanoic acid (Ru x (C 4 H 9 COOH) 0.30 ) which possess an intermediate crowded surface in comparison to RuNPs synthetized with ethanoic and octanoic acid. But also, it was observed that the longer the alkyl chain length, the lower will be the amount of carboxylates surrounding the ruthenium metal surface and also the higher will be the stability of the particles.

Moreover, according to theoretical DFT calculation the octanoic acid has the lowest adsorption energy onto the Ru 55 NP model, in comparison with pentanoic and ethanoic acid. In addition, to have favorable conditions for a ligand exchange reaction it is necessary that the exchanged ligand should have lower interaction strength with the RuNP than the incorporated moiety. For all these reasons, the chosen NPs system for studying the ligand exchange versus benzoic acid was the RuNPs prepared by 0.2 equiv. of octanoic acid in pentane, namely Ru x (C 7 H 15 COOH) 0.20 .

It is worth to note that the behavior of carboxylic acids is highly dependent on the solvent and that this can influence their acidic properties. In this case, in fact the benzoic acid has a slightly higher acidity (pKa = 4.2) than the octanoic acid (pKa = 4.9). [292] Nevertheless, it is expected these two acids have a sufficient difference in terms of interaction with the metal surface to observe a ligand exchange. Thus, this variable can be partially avoided due to the difference in pKa (< 1), and the real effect of the ligand exchange strength can be observed.

Roberto González Gómez 263 1D and 2D NMR spectroscopy ( 1 H & DOSY) was used to follow ligand exchange reactions at

RuNP surface between octanoic acid and benzoic acid, with the objective to estimate the quantity of ligands exchanged. For comparison purpose, a one-step synthesis of RuNPs using benzoic acid as a stabilizer was first performed in order to get the 1 H NMR signature of RuNPs stabilized by benzoic acid.

One-Step Synthesis of RuNPs Stabilized by Benzoic Acid

Owing to the reductive catalytic properties of RuNPs, it was suggested that the direct synthesis of RuNPs in the presence of photosensitizer could decompose the ligand (bpy based) and thus lose their photonic properties. On the other hand, it was observed that in some cases RuNPs can be stabilized with pyridine ligands, even when they are formed by following the organometallic approach using 3 bar of hydrogen. Therefore, a study of the RuNPs formation using benzoic acid as stabilizing agent was performed and followed by continuous 1 H-NMR experiments.

The synthesis of benzoic acid-stabilized RuNPs was carried out in a valved NMR tube dedicated to high pressure experiments with the aim to follow the decomposition of the [Ru(COD)(COT)] and in parallel the formation of the RuNPs. The experiment consisted in the reduction of the organometallic precursor in the presence of 0.2 equiv. of benzoic acid (L/[Ru]) under 3 bar of H 2 using deuterated THF as a solvent. The reaction was performed at low temperature (-15 °C), in order to decrease the reaction kinetics, for 24 h (scheme 4.1).

Roberto González Gómez 264 In order to assure a total decomposition of the metal precursor in the absence of stirring, the NMR tube was repressurized with 3 bar of H 2 , each 4 h (three times). The formation of the RuNPs was visually detected with time via a gradient of color from the top to the bottom of the NMR tube.

By 1 H NMR, it was observed the appearance of a signal at ca. 1.5 ppm corresponding to the cyclooctane released from the decomposition of the [Ru(COD)(COT)] while the reaction time advanced. In parallel, the signals of the benzoic acid (aromatic and alkyl proton range) became broader with time. The broadening of this aromatic proton signal was attributed to the proximity of the ligand with the metal surface. However, other signals at ca. [1.2 -1.4 ppm], also appeared that correspond to alkyl protons. Finally, in the last spectrum it was possible to assign this signals to cyclohexyl methanol [293] (figure 4.3). The presence of it can be explained by the hydrogenation of the benzoic acid.

Roberto González Gómez 265 Roberto González Gómez 266 From these [START_REF] Züttel | Hydrogen as a Future Energy Carrier[END_REF] H NMR results, it can be concluded that the formation of RuNPs happened and that the benzoic acid ligand was reduced. But these data do not provide information on the quantity of benzoic acid reduced. It can be totally or partially decomposed.

As a consequence, the ligand exchange strategy becomes a reliable methodology for the incorporation of aryl ligands onto the RuNPs surface.

Titration of Octanoic vs Benzoic Acid Ligand Exchange at RuNPs Surface

As announced before, the RuNPs chosen for the ligand exchange studies are those stabilized by 0.2 equiv. of octanoic acid (OcAc). The experimental titration done by NMR on this system of Ru x (C 7 H 15 COOH) 0.20 NP indicated that ca. 23.5 octanoates lie on the NP surface being strongly coordinated while approximately 6.5 octanoates are in an outer shell, interacting with the metal surface in a weaker manner.

For the titration experiment, the Ru x (C 7 H 15 COOH) 0.20 NPs were dispersed in deuterated benzene inside an NMR tube. Then, an increasing quantity of benzoic acid (BAc) was added in the

Roberto González Gómez 267

NMR tube (0.05, 0.10, 0.20 & 0.30 equiv.). After, the tube was plunged in an ultrasound bath for 30 min (scheme 4.2). Given the differences in the located proton signals (aromatic an alkyl proton range) for octanoates and benzoic acid, one of the best techniques to analyze the possible ligand exchange is the 1 H-NMR. Thus, each time that the benzoic acid is added into the reactor, new sharp signals should appear at low field without changing the observed peaks of the octanoates moieties if a ligand exchange or addition is not presented. However, a positive indication of a ligand addition will be found if some broad peaks are observed at low field, without changing the signals at high filed. Meanwhile, a ligand exchange will be found if both regions are modified.

From the first addition of BAc, namely 0.05 equiv., an evolution of the spectrum of the RuNPs was observed. Indeed, the signals of the coordinated octanoic acid protons (high field broad signal) started to change showing a decrease of their broadness. In parallel narrow peaks appeared at position corresponding to those expected for octanoic acid thus indicating that

octanoic acid has less interaction with the metal surface. This phenomenon amplified while increasing the quantity of benzoic acid added as clearly observed until addition of 0.20 equiv. of benzoic acid, which indicates the release of certain amount of octanoic acid to the solution.

However, it is important to point out that not all the octanoic acid ligand was released since broad signals are still visible even after addition of 0.30 equiv. of benzoic acid into the setup (figure 4.5 high field).

Looking at the low field part of the spectra, apart from the sharp signal of benzene at ca.

Roberto González Gómez 269

From these NMR data, it can be concluded that the addition of benzoic acid into the solution of Ru x (C 7 H 15 COOH) 0.20 NPs provoked the release of octanoic acid to the reaction medium and most probably the coordination of benzoic acid onto the RuNPs surface. Meaning that the ligand exchange was presumably done. H NMR allowed to evidence the dynamism of carboxylic acid ligands at the NPs surface when adding benzoic acid in a NMR tube containing octanoic acid-stabilized RuNPs. A ligand exchange was observed but the obtained data did not allow us to conclude about the real interaction of benzoic acid with the metal surface neither and about the quantity of ligand exchanged and released. In order to solve these questions, another type of NMR study needs to be performed.

DOSY-NMR was thus selected in order to get more information about the dynamic behavior of the ligands involved in the exchanging process. As described in section 3.2.5.3, this technique was expected to provide information on the interaction strength of the ligands with the RuNPs. In this way, it can be corroborated the inclusion of ligands at the metal surface or their release.

The diffusion-filtered 1 H-NMR spectra recorded at different quantity of added benzoic acid are given on figure 4.6. Broad signals are seen in alkyl and aromatic protons regions as previously observed in the 1 H-NMR spectra. Due to their broadness, the signals between [0.7 -2.5 ppm] can be assigned to alkyl protons that have low motion, thus to rigid octanoates molecules. In the aromatic region, the broad signal observed in the range of [6.5 -8.3 ppm] can be assigned to benzoic acid that is in interaction with the metal surface. Thus, a certain amount of octanoic and benzoic acids are strongly interacting with the RuNPs.

But when looking at the spectra evolution with the increasing quantity of benzoic acid added it can be observed at high field a continuous diminish of the signals for coordinated octanoic acid ligands up to the addition of 0.2 equiv. of BAc but no more evolution after the last addition (0.3 equiv.). This indicates that up to the addition of 0.2 equiv. of BAc, octanoates were released but some still remained, and the BAc cannot displace them. Meanwhile, at low field, an increase of the signal of benzoic acid is noted for each step of the experiential process, meaning a continuous coordination of the benzoic acid onto the RuNPs surface.

Roberto González Gómez 270 These NMR data highlighted that the addition of benzoic acid to a suspension of octanoic acid-stabilized RuNPs induced the release of octanoic acid in solution but not of all coordinated ligands. Benzoic acid is thus able to displace octanoates but not totally, even when forcing its concentration by adding it in more than the initial quantity of octanoic acid used for the preparation of the particles (see data for 0.3 equiv. of added BAc). Benzoic acid is thus not able to replace all the octanoates, probably for sterical hindrance reasons.

However, these results are of interest because they show that the addition of an aromatic carboxylic moiety can be done at the surface of RuNPs previously stabilized with an alkyl carboxylic acid. The combination of these two NMR experiments reinforce the selected approach to incorporate photosensitizers at the surface of RuNPs, due to the observed ligand exchange between the studied moieties.

CHAPTER IV

Octanoic Acid vs Benzoic Acid Roberto González Gómez 271 In order to know the ligand exchange efficiency, the next logical step will consist in a quantitative estimation of the exchanged ligands.

With the aim to get a titration of the surface ligands, namely of carboxylic and benzoic acid molecules strongly and weakly interacting with the nanoparticles, 2D-NMR DOSY analyses were carried out as previously described in section 3.2.5. The diffusional attenuation could be fitted with a Stejskal-Tanner equation by using a biexponential analysis for both the alkyl and aromatic proton regions. This indicated the presence of two different types of molecules interacting with the RuNPs surface for each proton region, namely with strong (D s ) and weak interaction (D w ). As a consequence, two different diffusion coefficients (D) were extracted for each proton type and related with their corresponding signal contribution (weight; table 4.1). was not affected by the ligand exchange and its metal structure remains the same during the whole process. This assumption will be later corroborated by TEM analyses.

Also, It is noteworthy that the signal contribution of the strongly bonded octanoic acid decreases with each new addition of benzoic acid. Meanwhile, the diffusion coefficient of the weak interacting octanoic acid (D w ) going toward the value of free ligand (D OcAc = 1.3 x 10 -9 m 2 .s -1 ), which means that there is more quantity of "free" exchanged ligand. These phenomena can be interpreted by a continuous decrease of the quantity of strongly coordinated octanoates.

Finally, the diffusion coefficient values for both strongly and weakly interacting benzoic acids did not significantly evolve during the study. But if the contribution of the signal for the benzoic acid strongly bonded appeared high at the beginning of the study, it decreased significantly when adding 0.

Roberto González Gómez 273

The addition of benzoic acid to the preformed nanosystems cause the release of octanoic acid from the metal surface and the incorporation of benzoic acid on it. This criterion can be clearly be observed by a decrease of the calculated quantity of strongly bonded octanoic acid (I s ) after the addition of 0.1 equiv. of benzoic acid. This value remains quite stable after. The number of strongly bonded benzoic acid does not evolve so much also. This can be seen that after a certain point, it becomes impossible to add more ligand at the NP surface, thus the exchange is low.

The addition of higher quantity of benzoic acid seems to The same variable shows provoke a saturation of the outer shell of ligands and the release of more adsorbed species. As it can be seen for the continuous increase of the quantity of benzoic acid weakly bonded (I w ; 3.1 -10.5 molecules) and the stabilization of the same variable but for octanoic acid (6.5 molecules) till 0.30 equiv. of benzoic acid is added into the setup (4.8 molecules).

The release of the octanoic moieties can be corroborated by the information of the "free" fast exchanging ligand (I f ), which increase for each addition step. The same variable shows the same trend for the benzoic acid, indicating that till certain point no more ligand can be exchanged or added onto the RuNPs surface and remains as "free" exchanging ligand.

These data provide interesting information on the ligand exchange ratio, meaning on the quantity of octanoic acid released vs that of benzoic acid incorporated (OcAc I s released / BAc I s incorporated). For the same quantity of the two ligands present in the reaction medium, that is after addition of 0.20 equiv. of benzoic acid added vs Ru x (C 7 H 15 COOH) 0.20 , the obtained ratio is 1.3.

Because 10.4 OcAc molecules are released and 7.9 BAc are incorporated. This ratio indicates that the quantity of octanoic acid released is superior to the quantity of benzoic acid incorporated.

Thus, the RuNPs surface is probably less crowded. This can be explained by the fact that benzoic acid has more steric hindrance and needs more place to be coordinated. But benzoic acid may be also a stronger stabilizing agent for which less molecules are needed to cap the RuNPs.

As a conclusion, it can be seen that the addition of the aryl ligand can remove certain quantity of octanoic acid from the RuNPs but at the end only around 37.6 % ([⅓ -⅖]) of the capping ligand are composed of benzoic acids and the rest as octanoic acids (13.1 OcAc vs 7.9 BAc). In order to corroborate that the octanoic acid was released into the reaction medium, a NOESY analysis has been performed for each step of the experiment (see section 6.1.3.6.3). Figure 4.8 presents the spectrum corresponding to the addition of 0.05 equiv. of benzoic acid to the colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 NPs.

It can be observed that even at this low amount of benzoic acid added, octanoic acid has been released and that it does not present any interaction with the RuNPs (figure 4.8 positive NOE in blue), supporting the ligand exchange previously described by other NMR techniques.

To remember, the positive NOE can only be observed when small molecules are free in the solution, meaning that they are not part of the inner or outer shell of the RuNPs.

Roberto González Gómez 275 DOSY analyses shown that the diffusion coefficient of the strongly bonded ligand (D s ) remains quite similar during the whole ligand exchange experiment. Thus, it is expected that the RuNPs did not suffer any size or morphology modifications. However, it is important to corroborate the surface state of the nanosystem by TEM analysis.

After these NMR studies that showed the ligand exchange taking place at the NP surface, one question arises about the evolution of the particles in terms of size or/and shape. DOSY analyses shown that the diffusion coefficient of the strongly bonded ligand (D s ) remains quite similar during the whole ligand exchange experiment. Thus, it is expected that the RuNPs did not suffer any size or morphology modifications. However, it is important to corroborate the surface state of the nanosystem by TEM analysis in order have a better answer to this question.

The TEM analysis has been performed after the last step of the ligand exchange study (addition of 0.30 equiv. of benzoic acid) and the results were compared to the TEM data of the The experimental tools used to follow the ligand exchange experiments evidenced that benzoic acid could be incorporated at the surface of octanoic acid pre-stabilized RuNPs through the release of octanoic acid molecules from the metal surface, up to a certain quantity, without observing any reduction of the aryl ligand. In the reaction conditions applied, the exchange was not complete, but it could be estimated that at least ca. ([⅓ -⅖]) of the RuNPs surface was covered by benzoic acid. TEM analysis showed no evolution of the NP morphology thus indicating a good stability of the particles. These results point out it is possible to introduce a second carboxylic acid like benzoic acid at the surface of octanoic acid-stabilized RuNPs without modification in morphology and size of the particles.

Roberto González Gómez 277

There are two main parameters to consider in order to explain the ligand exchange observed, namely steric hindrance and acidity (figure 4.10). Benzoic acid having higher steric hindrance than octanoic acid it is expected to occupy a higher bulk volume at the NP surface. This means, it can be difficult for benzoic acid to coordinate onto a crowded NP surface as it was the case for the initial Ru x (C 7 H 15 COOH) 0.20 NPs (figure 4.10 a).

Thus, the driving force for the ligand displacement observed may arise from the difference in acidity between the two types of carboxylic acids. Indeed, benzoic acid displays an acidity five times higher than that of octanoic acid. This suggests that the benzoate form is easier to get than the octanoate one. Thus, when benzoic acid was added into the colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 NPs, an acid-base exchange may have happened, thus weakening the adsorption energy of the octanoate and provoking its release which probably allowed the benzoate to coordinate at the metal surface (figure 4.10 b).

These processes are interdependent and the fact that not all octanoates were replaced indicates that the affinity of the benzoic acid onto the RuNPs is quite similar to that of octanoic acid or even slightly lower due to the exchanging ratio. It is thus more reasonable to propose an equilibrium between the two carboxylate species that can be governed by steric reasons. This is illustrated on figure 4.10 a.

Roberto González Gómez 278 The results of this ligand exchange study indicate that such a strategy may be followed in order to achieve the anchoring of a photosensitizer bearing pending carboxylic acid groups at the surface of pre-formed RuNPs stabilized by octanoic acid and probably also in the case of pentanoic acid-stabilized RuNPs. Doing so, it can be expected to have at least a certain amount of the PS grafted onto the metal surface and thus to get a hybrid nanomaterial for the target water-splitting reaction.

The next section will provide theoretical calculation results that were performed in order to understand better the ligand exchange reaction.

Roberto González Gómez 279

DFT Modelling of the Involved Species in the Ligand Exchange

The ligand exchange between interacting molecules with a metal surface is expected to be possible only if the exchanged ligand has a lower affinity with the metal surface than the incorporated moiety. In other words, it is expected from the new capped ligand to better stabilize the NPs or the ligand exchange phenomenon will not be able to be achieved. [START_REF] Hurst | N-Heterocyclic carbene coated metal nanoparticles[END_REF] The stability granted by a capping ligand to the metal surface can be related to its adsorption energy. [START_REF] Meng | Water adsorption on metal surfaces: A general picture from density functional theory studies[END_REF] In order to study the affinity of both octanoic and benzoic acids with the ruthenium surface, the protonated and deprotonated carboxylic species involved in the ligand exchange experimentally studied were deposited onto the (001) plane of the Ru 55 NP model (see section 6.2.1). Then a periodic DFT optimization was performed for each studied system (see section 6.2.2) and the ligand adsorption energy obtained for each capping ligand (see section 6.2.3). The obtained values are presented in section appendix B.3 and corresponding coordinates in section appendix F.

The carboxylic acid isomers considered in the structures reported in Figure 4.11 are not the most stable one. In the ethanoic acid case, the presented structures for the adsorption of carboxylic acids are more stable (7.7 kcal.mol -1 ) when the acid proton rotated 180° in order to have higher interaction with the metal surface (E ads-bi-H = -16.2 kcal.mol -1 E ads-bi-H 180° = -23.9

kcal.mol -1 ).

As it was observed from previous carboxylic acid ligands analyses, the most stable configuration is the carboxylate form (figure 4.11) due to the low activation energy of the O-H bond (see section 2.4.1). ) are also presented.

Comparing the adsorption energies of the deprotonated moieties, it was observed that the benzoate stabilizes the Ru 55 NP 10.2 kcal.mol -1 more than the octanoate adsorbed in the same Ru 55 NP (001) plane. This preliminary result, although obtained on a bare surface, is in favor of positive octanoate vs benzoate ligand exchange owing to higher stability that the benzoate is expected to provide to the metal system.

Previously, it was proposed two parameters susceptible to influence the ligand exchange onto preformed RuNPs, namely acidity and steric hindrance. The acidity can be discussed on the basis of DFT adsorption energy values calculated for protonated and deprotonated carboxylic entities. These data completed by the inductive effect provided by the aryl group in benzoic molecule, lead to a stronger electron donor property for the benzoate in comparison with the octanoate (electronic effects). Thus, this could explain the values observed for the adsorption energies of the carboxylate moieties. Therefore, at this stage, the benzoate appears as a better stabilizer and the exchange of octanoate by benzoate should be favored.

However, the steric effects between ligands plays an important role to determine the surface composition of the Ru 55 NP and thus, corroborate the viability of a ligand exchange. [START_REF] Nishigaki | A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster[END_REF] Indeed the blockage of binding sites by coordinated ligands can prevent the adsorption of new

Roberto González Gómez 281 species, and even more when the incoming ligands have a higher steric hindrance than those already adsorbed. [START_REF] Rempel | Density functional theory study of ligand binding on CdSe (0001) ,(0001), and (1120) single crystal relaxed and reconstructed surfaces: implications for nanocrystalline growth[END_REF] Moreover, surface ligands have an effect on the electronic properties of the metal surface and, in the case of RuNPs, tend to weaken adsorption strengths. Therefore, a theoretical study was also performed on surface crowded nanoparticles. In order to describe a more trustworthy ligand exchange reaction (figure 4.12).

The

Roberto González Gómez 282

The DFT energies obtained for the optimized structures of figure 4.12 (see section appendix B.4), are summarized in table 4.3. These data can be used to determine the thermodynamically direction of a reaction in order to predict the viability of a ligand exchange. This DFT study does not represent the ligand exchange reaction as experimentally studied in section 4.2.2. Consequently, the optimized structures do not correspond exactly to the surface mapping found in the experimental study, and this study will be completed in the nearest future by considering the best surface coverage value according to the present DFT calculations.

However, a clear trend in the octanoic acid releasing vs the incorporation of benzoic acid can be seen. According to the DFT reaction energy results, the ligand exchange is thermodynamically favorable and viable in all described reactions (figure 4.13).

However, the subsequently addition of ligands to the Ru 55 NP stabilize the d-band center of the NP, [START_REF] Lima | Catalytic Activity -d-Band Center Correlation for the O2 Reduction Reaction on Platinum in Alkaline Solutions[END_REF] making it more stable. [START_REF] Pozun | A Systematic Investigation of p-Nitrophenol Reduction by Bimetallic Dendrimer Encapsulated Nanoparticles[END_REF] Thus, it is not possible to evaluate the real meaning of the DFT reaction energy for the first proposed reaction, where three more carboxylates were incorporated. However, the second reaction involves the addition of only one benzoate obtaining an energy stabilization of -85.02 kcal.mol -1 . This value is higher than for the adsorption of a single benzoate into Ru 55 bare NP, which is -58.8 kcal.mol -1 , considered as probable maximum adsorption value. Thus, it can be concluded that there is an electronic effect that makes the adsorption of benzoates more favorable than octanoates.

This phenomenon could be attributed to the higher sigma donation of the benzoic species and thus, higher retrodonation to the π* orbital, making it more stable in terms of electronic Roberto González Gómez 283 effects. In order to corroborate this assumption, it will be necessary to perform a COHP analysis and compare with Ru 55 NP fully covered by octanoates and/or benzoates.

The third reaction also involves the adsorption of one extra carboxylate but onto a more crowded Ru 55 NP. For this situation the obtained energy is -67.46 kcal.mol -1 which is closer to the adsorption of a single benzoate (-58.8 kcal.mol -1 ) but still greater. This means that the exchange is still favorable but it also indicates that the higher the coverage value, the lower the exothermicity of the exchange reaction.

This could be correlated to the steric hindrance effects previously proposed. Anyway, this conclusion was corroborated with the last reaction where even with the decrease of one carboxylate, less crowded surface, the reaction is still thermodynamically favorable. The obtained data can be analyzed as the average adsorption energy for all capped ligands. The data for the Ru 55 NP covered by octanoates were interpolated for the adsorption Roberto González Gómez 284 energies reported in section appendix B.2, meanwhile for the ligand exchange studied systems, the mean adsorption energy of the carboxylates is described in the section appendix B.4.

As a result, it was observed that, considering the ligand mean adsorption energy for the two systems, the stabilization is higher for the particle covered by a ligand mixture than when it is only covered by octanoates (table 4.4). For example, for the eleven adsorbed carboxylates, the Ru 55 NP covered by a ligand mixture is stabilized by ca. 4.5 kcal.mol -1 for each capped moiety.

Hence, the result shows that the benzoate has a higher affinity to the metal center and thus, the ligand exchange is possible. As a consequence, a more stable system was obtained but less reactive, as expected. In conclusion, the DFT results indicate that a certain amount of octanoic acid ligands can be replaced for benzoic acid ligands which induces the octanaote release to the reaction medium, which agrees with the experimental findings. Moreover, the theoretical approach evidenced that the benzoic acid has a better affinity for the Ru 55 NP due to electronic effects. However, as also estimated in the experimental titration, it was observed that [⅗ -⅔] of octanoates remain at the RuNPs surface. This indicates that the initial steric hindrance of the inner and outer shells presented in the experimental conditions (crowded Ru x (C 7 H 15 COOH) 0.20 NPs) plays an important role in the ligand exchange. In order to corroborate this steric effect more DFT calculations need to be performed.

Roberto González Gómez 285

Ligand Exchange at RuNPs Surface: Octanoic Acid vs

TFA

The ligand exchange experiments described before were carried out in order to study the possibility of introducing benzoic acid (aryl ligand) at the surface of RuNPs pre-stabilized by octanoates. Even so, the octanoate vs benzoate ligand exchange was not complete, the obtained results have shown that this strategy could be followed, thus opening the way to integrate a molecule of interest (bpy-based photosensitizer) at the surface of the particles via the same anchoring mode (carboxylic acid) for a target application (water splitting process).

It has been reported in the literature that the ligand exchange in nanomaterials can be affected for the acidity of the incorporated species. [START_REF] Barker | Ripening during magnetite nanoparticle synthesis: Resulting interfacial defects and magnetic properties[END_REF] This phenomenon has been observed in the frame of a ligand exchange involving a proton exchange, as it was the case in the previous study. It has been also observed that highly negative charged molecules often provide more stability to the NP surface thus making the facility to liberate the protons a key-point. [START_REF] Bian | Aggregation and dissolution of 4 nm ZnO nanoparticles in aqueous environments: influence of pH, ionic strength, size, and adsorption of humic acid[END_REF] As well, some stabilizing agents were observed to have different affinity properties with the metal surface depending on the acidity of the reaction medium. Hence, the ligand exchange ratio can be tuned via the acidity properties of the ligands or of the reaction medium. [START_REF] An | Fast synthesis of dopamine-coated Fe3O4 nanoparticles through ligand-exchange method[END_REF] In section 4.2, the ligand exchange between pre-stabilized RuNPs by octanoic acid and benzoic acid was shown possible but with a process efficiency lower than ca. 40.0 % (I s-BAc /I s-total ).

According to the obtained experimental and theoretical data, this low efficiency can result from the steric hindrance of the benzoic acid ligand, because its affinity and acidity appeared higher than those of the octanoic counterpart. Therefore, in order to force the coordination of a carboxylic acid ligand onto the RuNPs surface, it was decided to repeat the ligand exchange study by using of a smaller ligand that has a higher acidity. For this purpose, trifluoracetic acid (TFA) has been chosen.

Roberto González Gómez 286

Titration of Octanoic vs TFA Exchange on the RuNPs Surface

In order to analyze the influence of the acidity in the ligand exchange process at the surface of RuNPs stabilized by octanoic acid, an experiment as described in section 4.2.2 was performed. The RuNPs system chosen for this experiment was a sample of Ru x (C 7 H 15 COOH) 0.20 NPs synthetized in pentane after the addition of extra 0.20 equiv. of octanoic acid (OcAc). This system was selected in order to have a completely crowded RuNP surface and thus, observe the real potential of the acid through its acidic character and reduce the steric hindrance effect.

The TFA has a pKa of 0.2, a value of four orders of magnitude stronger than that of the initial attached ligand (OcAc; pKa = 4.9) . This difference results from the presence of three fluorine atoms in the ligand which renders the proton of the carboxylic acid highly acidic and its liberation easy. However, the presence of these halogens also reduces the electronic donor strength of the whole molecule. [START_REF] Difranco | Evaluation of Donor and Steric Properties of Anionic Ligands on High Valent Transition Metals[END_REF] Therefore, this system is suitable for observing the influence of the incoming ligand acidity (due to the probable acid-base exchanges onto the RuNPs surface) and removing the "affinity effect" in the ligand exchange process.

Previous titration experiment (see section 3.2.5. and ca. 6.5 carboxylates that are weakly interacting and present in an outer shell (l w ). After the addition of 0.2 equiv. of extra octanoic acid, a similar quantity of ligands was found in the outer and inner shells (ca. I s = 20.7; I w = 7.7). However, a high quantity (ca. 41 molecules) of free or exchanging ligand was observed. Therefore, this system is suitable for observe the influence of the acidity in the ligand exchange.

The sample of pre-formed RuNPs was redispersed in deuterated benzene inside an NMR tube under argon atmosphere. After, 0.10 equiv. of trifluoroacetic acid (TFA) was added and the NMR tube was plunged in an ultrasonic bath for 30 min at r.t. Scheme 4.3 provides a schematic representation of the ligand exchange reaction at the surface of the particles. 1 H, [START_REF] Roduner | Size matters: why nanomaterials are different[END_REF] F-NMR and DOSY analyses were then performed (see section 6.1.3.7.4). In these analyses, the grease present in the solution was used as internal standard.

Roberto González Gómez 287 The observation of narrower signals can be explained by the presence of higher quantity of octanoic acid in solution as the result of a release of octanoic acid from the metal surface. This is particularly highlighted when comparing the spectrum of the initial Ru x (C 7 H 15 COOH) 0.20 NPs with that recorded after addition of TFA. Moreover, there is still broadness in the region corresponding to octanoic acid which indicates that coordinated octanoic acid remains and the exchange was not complete.

Roberto González Gómez 288 NPs provokes a release of octanoic acid, but not totally. This means that the acidity properties of TFA allowed displacing some octanoates from the metal surface. Since, the chosen system was crowded, inner (ca. 20.7 molecules) and outer shell (ca.7.7 molecules) and full of octanoates in the reaction media (ca. 41 molecules), the effect of the steric hindrance is reduced and define that the acidity of these ligands is crucial in the ligand exchange process. The next logical question is how the TFA is interacting at the metal surface? In order to answer this question, a 19 F-NMR spectrum was recorded. 13 TFA molecules per RuNP that interact strongly with the metal surface (see table 4.6). Since, owing to technical issues, it was not possible to perform DOSY NMR for the fluorine isotopes. Thus, it was assumed that the rest of TFA is weakly interacting with the ruthenium surface, being either free in solution or in dynamic exchange. The estimated quantity of weakling interacting TFA is ca. 4.3 per RuNP.

Roberto González Gómez 290

With the aim to get a complete titration of the surface ligands, namely of octanoic acid molecules strongly and weakly interacting with the nanoparticles, 2D-NMR DOSY analyses were carried out as previously described in section 3. The diffusion coefficients found for two these two types of ligands are D s = 3.4x10 -10 m 2 .s -1

and D w = 1.4x10 -9 m 2 .s -1 , respectively. It is worth to note that the second coefficient value (D w ) is very similar to that obtained for free octanoic acid (1.3x10 -9 m 2 .s -1 ). This result indicates that there is a high quantity of free octanoic acid in the reaction medium, as expected for the release of octanoic acid into the reaction medium (table 4.5). The table 4.5 evidences the increase of the hybrid system mobility, represented for the increase in the diffusion coefficient of the strongly bonded ligand (D s ; 1.6x10 -10 to 3.4x10 -10 m 2 .s -1 ).

This result is represented as a diminish of the hydrodynamic diameter of the RuNPs system. Which is expected, since smaller particles (TFA) are included in the inner shell of the system and bigger particles are released (OcAc). However, it is possible that the metal core is digested for the acid or modified. Thus, a TEM microscopy needs to be performed in order to solve this question (vide infra).

From the extracted data of DOSY analysis (diffusion coefficients of the observed species and corresponding contribution) it could be determined the quantity of octanoic acid ligands surrounding the RuNPs (see section 6.1.3.7.2). This allowed to define a reliable surface mapping of the RuNPs obtained after the addition of TFA (table 4.6). The data in table 4.6 show that the final RuNPs have a higher quantity of carboxylates (ca.

five carboxylic molecules) that surround the inner shell. It appears that ca. 8.4 octanoates have been removed from the NP surface while 13 trifluoroacetates were incorporated. This result evidences that a higher number of trifluoroacetates (ca. 13/8.3 = 1.56) were coordinated compared to the number of octanoates released. This result can be attributed to the lower steric hindrance of TFA compared to that of octanoic acid.

It also highlights an increase of the surface coverage in the presence of TFA ligands. It is worth to mention that these results were obtained using only a small amount of ligand (0.10 equiv.) compared to the total quantity of octanoic acid present in the reaction medium (0.4 equiv.). This thus evidences the higher affinity of TFA for the ruthenium surface compared to octanoic acid, probably for a combined effect of acidity and steric hindrance.

In order to compare the ligand exchange reaction depending on adding either benzoic acid or trifluoroacetic acid onto RuNPs pre-stabilized with octanoic acid, data obtained for the addition of 0.10 equiv. of each incoming ligand have been reported in table 4.7. These data clearly reflect the different behavior observed for the two carboxylic acids added.

Roberto González Gómez 293 From these data, it can be seen that the experiment performed by adding TFA led to the coordination of more trifluoroacetates than the number of benzoates incorporated (ca. 13.0 vs 7.1). This was accompanied to the release of less octanoates in the reaction medium. Given the lower pKa of trifluoroacetic acid compared to benzoic acid it can be expected that this carboxylic acid will have more ability to be introduced and exchange onto the RuNPs surface. But also, the higher number of TFA incorporated at the metal surface indicates the positive influence of the lower steric hindrance of this carboxylic acid compared to octanoic acid.

All together these observations, it can be proposed that both acidity and steric hindrance of the incoming ligand play a role in the exchange reaction. In the present comparative studies, for a same quantity of added ligand (0.10 equiv.) these two factors favored the coordination of more trifluoroacetates than octanoates at the surface of pre-stabilized RuNPs by octanoic acid.

Complementary experiments would be to start from octanoic acid-stabilized RuNPs reacted with benzoic acid and then add TFA.

It has seen that the whole effects of TFA have led to a surface coverage of the final NPs with a higher quantity of added ligand. Even when TFA is thus a better exchanging ligand than benzoic acid, for the two systems, in the experimental conditions applied, it was not possible to remove all the octanoic acid. Therefore, more studies of the ligand exchange with TFA need to be done in order to try to release all the octanoates and get RuNPs with only TFA at their surface.

The RuNPs were exposed to a strong acid ligand in the ligand exchange process. Thus, it is possible that the system suffers a metal ripening [START_REF] Ranjan | Metallic Nanocrystal Ripening on Inorganic Surfaces[END_REF] due to the change strength of the binding molecules. [START_REF] Fiurasek | Phosphonic and Sulfonic Acid-Functionalized Gold Nanoparticles: A Solid-State NMR Study[END_REF] This hypothesis can be reinforced due to the decrease of the hydrodynamic diameter observed by DOSY analysis (D s ; 1.6x10 -10 to 3.4x10 -10 m 2 .s -1 ).

CHAPTER IV

Octanoic Acid vs TFA Roberto González Gómez 294

Thus, one question arises about the fate of the particles in terms of size or/and shape. To answer this question, TEM analysis was performed from the reaction mixture obtained after addition of 0.10 equiv. of TFA.

The TEM images obtained were compared to those of Ru However, a slightly different morphology was noticed. Indeed, the final particles seem to be more ill-defined, looking more elongated than spherical. But these results allowed to conclude that the morphology of RuNPs did not change importantly during the ligand exchange study. In conclusion of this part, a ligand exchange was achieved between octanoic acid and TFA that led to the release of octanoic acid and the coordination of TFA at the RuNP surface. No significant modifications of the RuNPs is terms of morphology and mean size have been observed.

The exchange process was possible without adding a high quantity of incoming ligand. And even Roberto González Gómez 295 more important the efficiency of exchange was observed to be higher than in the case of the exchange with benzoic acid. More trifluoroacetates were incorporated at the surface of the RuNPs compared to benzoic acid case. However, the exchange was not total and some octanoates remained at the surface of the RuNPs as already seen with benzoic acid.

All together the results obtained indicate that both the acidity and steric hindrance of the incoming ligand play a role in the ligand exchange process. But it cannot be assured that these variables are the only ones involved in the increase of the ligand exchange efficiency observed with TFA. Indeed, it can be expected that the inductive effect of TFA due to the fluorine atoms (ligand affinity strength) affects also the process. However, with the data in hand it is clear that the TFA is a better ligand for exchanging with octanoates than the benzoic acid.

In the next section, the observed ligand exchange and the role of the acidity and steric hindrance will be briefly discussed in terms of DFT calculations.

DFT Modelling of the Involved Species in the Ligand Exchange

As described in previous sections, the incorporation of a new capping ligand at the surface of preformed RuNPs involves that the incoming ligand possesses a higher affinity towards the metal surface, than the initial one. Meaning that the new ligands are better stabilizing agents. [START_REF] Hurst | N-Heterocyclic carbene coated metal nanoparticles[END_REF] The experimental studies have shown that the addition of TFA gave rise to better ligand exchange ratio than the benzoic acid did. This effect was attributed to both the acidity and its steric hindrance of the TFA. However, one can also expect electronic effects in a ligand to influence the affinity of the molecule towards the surface of the RuNPs. This inductive effect of benzoic acid was discussed in section 4.2.3 and found to be quite important for the ligand exchange process and the stabilization of the particles.

The presence of three fluorine atoms in the TFA molecule induce a high acidity. Thus, a high rate for its deprotonation can be expected and so its fast coordination at the NP surface as carboxylate. However, TFA has a low sigma donor strength due to the inductive electronic effects provided by the fluorine atoms (attractive effects). [START_REF] Difranco | Evaluation of Donor and Steric Properties of Anionic Ligands on High Valent Transition Metals[END_REF] Therefore, the absorption energy of this Roberto González Gómez 296 molecule onto the Ru 55 NP model should be very useful in order to clarify its affinity towards the surface of RuNPs.

A similar procedure as previously described for benzoic acid was performed in order to estimate ligand affinity with the ruthenium surface (see section 4. ) are given for each case.

The values of adsorption energy obtained show that, for the considered adsorption plane, the trifluoroacetate has a higher affinity than octanoate given the observed difference of ca.

11.0 kcal.mol -1 . This preliminary result clearly confirms that a ligand exchange is possible between these two ligands and that it is slightly in favor of the coordination of trifluoroacetate.

Looking at the adsorption energy calculated for benzoate and trifluoroacetate, one can see that they are not significantly different (> 1 kcal.mol -1 ). Therefore, from these data, it is not possible to discuss about any difference in the electronic effects of benzoate and trifluoroacetate.

Roberto González Gómez 297 Thus, if was observed that TFA led to a more efficient ligand exchange vs octanoic acid than benzoic acid did (see section 4.3.1), this behavior cannot be explained by their different adsorption energy strength (electronic effects). Therefore, the acidity and steric hindrance are crucial to explain the ligand exchange phenomenon experimentally observed.

All the results evidence that several parameters are implicated in the efficiency of the ligand exchange like acidity, steric hindrance and electronic effects. With the aim to be able to conclude more precisely on the importance of each parameter, more DFT calculations are required.

Conclusion

After the full characterization of RuNPs stabilized with different carboxylic acids bearing an alkyl chain (ethanoic, pentanoic and octanoic acid), the mapping of their surface (capping ligand titration) and the specification of their electronic properties, it was described in this chapter the reaction of a higher acidic carboxylic acid with pre-formed RuNPs synthesized with octanoic acid.

The main objective of this study was to determine if a second carboxylic acid can be anchored at the surface of pre-stabilized RuNPs. This reaction was chosen as a model reaction with the aim to define if it can be an interesting strategy to graft a photosensitizer having pending carboxylic acid groups at the surface of pre-formed RuNPs in order to get an hybrid nanomaterial for testing in the water-splitting process.

The chosen photosensitizer is based in bipyridines ligands, that can be suitable to be reduced in the presence of RuNPs catalyst and hydrogen. Therefore, a direct synthesis of RuNPs in the presence of the photosensitizer as stabilizing agent under hydrogen pressure (organometallic approach) was not performed, due to the ligand bipyridine reduction risk.

This assumption was corroborated by the direct synthesis of RuNPs in the presence of benzoic acid as stabilizing agent. In this experiment, it was observed the partial and total reduction of the aryl ligand. Therefore, another strategy needs to be selected for including the photosensitizer onto the RuNPs surface. The chosen strategy was the ligand exchange.

Roberto González Gómez 298

For this purpose, in the first part of this chapter, preformed RuNPs stabilized with 0.20 equiv. of octanoic acid were first exposed to an increasing certain quantity of benzoic acid. The obtained nanosystems were characterized by NMR techniques and DFT tools. The combination of these approaches provided fruitful informations of the efficiency of the chosen strategy.

As a result, it was found possible to remove a certain quantity of the octanoate ligand and to incorporate benzoic moieties at the RuNPs surface without modifying the size and the morphology of the preformed RuNPs. According to the obtained results this exchange process was found to be favorable owing to a combination of effects, namely electronic, steric hindrance and probably acidity effects of the incoming ligand Even when the process was achieved, it was not total. Indeed, only ca. [⅓ -⅖] of the octanoates initially coordinated at NP surface were replaced by benzoates, and the addition of higher quantity of benzoic acid did not increase the ligand exchange ratio. DFT calculations supported the viability of the ligand exchange as the result of electronic effects (higher adsorption energy in bare and crowded Ru 55 NP and thermodynamically spontaneity of the ligand exchange reactions). However, it was thought probable that the efficiency of the exchange process is affected by the steric hindrance of the ligands.

It is worth to point out, that the two approaches (experimental and theoretical) have a high degree of agreement in the characterization of this strategy. But in order to explain all the experimental finding and the difference in the electronic effects between the exchanged molecules, more DFT calculations need to be performed.

Hence, it can be said that the ligand exchange is a good methodology to be followed in order to include the photosensitizer onto preformed RuNPs, without reducing the inserted molecule and thus, conserving its photonic properties.

The second part of this chapter focused on a second ligand exchange study, keeping the octanoic acid pre-stabilized RuNPs and using this time trifluoroacetic acid as incoming ligand. The choice of trifluoroacetic acid (TFA) was based on its higher acidity and lower steric hindrance compared to those of benzoic acid.

It was found that TFA has a better efficiency in the ligand exchange process than the benzoic acid. The experimental titration results indicated that the surface of preformed Roberto González Gómez 299

Ru x (C 7 H 15 COOH) 0.20+0. 20 NPs can be modified by substituting a slightly more than the half of the initial capping ligands by trifluoroacetates by adding only 0.10 equiv. of TFA. Also, the surface of the modified RuNPs was observed to display a higher quantity of carboxylic ligands, thus highlighting a clear effect of the low steric hindrance of TFA On the basis of a significant difference of adsorption energy values (ca. 11.0 kcal.mol -1 ) between octanoate and trifluoroacetate, DFT calculations provided insights of the favorable situation with TFA, a ligand exchange. Nevertheless, the theoretical results pointed out that there is no significant variation between the adsorption energy of the benzoate and the trifluoroacetate.

As a consequence, the difference in the ligand exchange ratio observed between the benzoic acid and TFA vs octanoic acid cannot be easily explained. More DFT calculations need to be done to elucidate the driving force of this different behavior.

All together the obtained results underline that for the ligand exchange process, not only the electronic effects play and important role, but also the steric hindrance and the acidity of the incorporated ligand. It is worth to point out, that once more the two approaches (experimental and theoretical) have shown a high degree of agreement in the evaluation of the ligand exchange strategy. But in order to explain all the phenomenon, more DFT calculations are required

To conclude, the carboxylic acid exchange studies performed allowed to evidence that the grafting of a photosensitizer with free carboxylic acid groups at the surface of preformed RuNPs may be realized by following a ligand exchange strategy. But several parameters (like acidity, steric hindrance or electronic effects) have to be taken into account for the exchange to be favorable.

However, even if one can expect the process to not be highly effective, at least a few molecules of photosensitizer should be incorporated at the RuNP surface which should allow to build the desired hybrid catalytic material for evaluation in water-splitting.

In the next and last chapter of results in this PhD manuscript, theoretical data about the grafting of a ruthenium polypyridyl complex, namely a photosensitizer (PS) onto preformed RuNPs will be presented.

Roberto González Gómez 303

Introduction

Photosensitizers (PS) are often described as light activated compounds which produce a photochemical change in an adjacent moiety. PS are initiators of a chemical reaction by facilitating energy transfer (solar to chemical) that allows the reaction to happen. When activated by light, photosensitizers are able to transfer electrons to another molecule by following a type I mechanism. [START_REF] Allison | Photosensitizers in clinical PDT[END_REF] The effectivity of such a process depends on several parameters such as the chemistry of the photosensitizer, absorption wavelength, light intensity, etc.

The photosensitizers have been widely employed in photodynamic therapy (PDT) for cancer treatment and drug delivery systems. Scientific community has focused its efforts in improving the efficiency of the procedure. Several publications have reported the use of a hybrid material (photosensitizer + nanoparticles) in order to increase the capability and selectivity of the material in the PDT. [START_REF] Bechet | Nanoparticles as vehicles for delivery of photodynamic therapy agents[END_REF] The functionality of MNPs in this hybrid material (PS + MNPs) can be divided into passive carriers or active participants in the PS excitation. Passive nanoparticles (like AuNPs) have been used as pure carrier of PS or applied as encapsulating material for drug delivery (such as iron oxide nanomaterials). Meanwhile, active nanoparticles are used to transfer energy to produce reactive oxygen species (CdSe) or to transduce low energy light to higher energetic emissions ([Y]:Yb). [START_REF] Kumar | Nanoparticles in photodynamic therapy: An emerging paradigm[END_REF] The combination of photosensitizers and nanoparticles produce new hybrid materials that combine their properties to increase the functionality, selectivity and effectivity in PDT and several other applications ranging from medicine [START_REF] Huang | Photosensitizer-conjugated magnetic nanoparticles for in vivo simultaneous magneto fluorescent imaging and targeting therapy[END_REF] to energy storage. [START_REF] Lahav | Photoelectrochemistry with Integrated Photosensitizer-Electron Acceptor and Au-Nanoparticle Arrays[END_REF] In fact, some types of nanoparticles, can be used as photosensitizer by itself, like quantum dots. [START_REF] Bakalova | Quantum dots as photosensitizers?[END_REF] Porphyrins, naphtalocyanines, chlorins, pthalocyanines are some of the photosensitizers widely used in the industry and academia. [START_REF] Allison | Photosensitizers in clinical PDT[END_REF] Also, pyridine-based (bpy) photosensitizers in combination with several metal centers, is another family of well-studied compounds specially used for the production of hydrogen from water. [START_REF] Ferrere | Photosensitization of TiO2 by [FeII(2, 2'-bipyridine-4, 4 '-dicarboxylic acid)2(CN)2]: band selective electron injection from ultra-short-lived excited states[END_REF] Pyridine-based ruthenium organometallic compounds (figure 5.1) were developed as an inexpensive dye sensitized for solar cells, which exhibits a light to electrical conversion efficiency Roberto González Gómez 304 of 10 %. [START_REF] Zakeeruddin | Design, synthesis, and application of amphiphilic ruthenium polypyridyl photosensitizers in solar cells based on nanocrystalline TiO2 films[END_REF] Also, they have large extinction coefficients that allow the detection of donor-acceptor reactions a low sensitizer concentration. [START_REF] Number | New photosensitizer. Tris (2,2'-bipyridine) ruthenium (II) chloride[END_REF] Figure In these ruthenium polypyridyl complexes, a metal-to-ligand charge transfer of the triplet excited state can happen. In principle, this phenomenon can happen even if there is just one bipyridine in the organometallic compund, but it can be magnified and assured if more bipyridine units are present. [START_REF] Bignozzi | Simple poly (pyridine) ruthenium (II) photosensitizer:(2, 2'-bipyridine) tetracyanoruthenate (II)[END_REF] However, these compounds are not highly-effective at high wavelength and the incorporation of a fluorescent ligand in the structure of Ru-bpy based photosensitizer can provide a wider range of applications. [START_REF] Carrone | Fluorescent Ligands and Energy Transfer in Photoactive Ruthenium-Bipyridine Complexes[END_REF] Ruthenium bipyridine-based photosensitizers have been extensively used for the generation of hydrogen by the water splitting process. More recently, their association with metal NPs into hybrid [PS]-NP nanomaterials showed to be an interesting strategy to produce hydrogen from water. [START_REF] Ponder | Surface chemistry and electrochemistry of supported zerovalent iron nanoparticles in the remediation of aqueous metal contaminants[END_REF] Such hybrid nanomaterials are expected to present high catalytic activity owing to the high surface to volume ratio of the catalyst part (nanoparticle) that will be able activated due to the light harvesting PS part. A key point may be the connection between the two parts of the hybrid nanomaterial, the PS and the NP. It is thus required to have at disposal an effective methodology to anchor the photosensitizer at the surface of metal-based nanoparticles. This can be achieved by using carboxylic acids as grafting groups. [START_REF] Kathiravan | Effect of anchoring group on the photosensitization of colloidal TiO2 nanoparticles with porphyrins[END_REF] Roberto González Gómez 305 Owing to the results obtained in previous chapter regarding the exchange of carboxylic acids at the surface of pre-formed RuNPs. It was envisaged to apply this strategy in order to anchor a ruthenium complex at the RuNPs surface. In this chapter, it will thus describe the DFT analysis performed in order to probe the coordination of a polypyridyl ruthenium complex containing a bipyridine functionalized with carboxylic acid groups [START_REF] Donnell | Photoacidic and Photobasic Behavior of Transition Metal Compounds with Carboxylic Acid Group(s)[END_REF] at the surface of ethanoatestabilized RuNPs. For this purpose, it was used the same theoretical tools as previously described in other chapter of this PhD manuscript (see chapter IV).

The main objective of this study was to determine if the coordination of the ruthenium complex is feasible or not by this route. A schematic representation of the study performed is given in figure 5.2. Modelling of MNPs and its relationship with different covered ligands is the principal tool in this PhD thesis to elucidate the electronic properties of the RuNPs stabilized with ethanoic acids (see chapter II). Thus, it was possible to build a reliable Ru 55 NP model that provides trustful insights due to their high agreement with the experimental findings. By using this model, it was plausible to describe general properties of the RuNPs. Also, it was possible to titrate the number of capping ligands surrounding the nanosystems, its molecular composition (deprotonated), its reliability for the HER reaction, etc.

Once the model was corroborated to be a reliable source of information, it was feasible to extrapolate the gathered information to a Ru 55 NP model capped with more flexible and longer alkyl chain ligands (pentanoic and octanoic acid, see chapter III). Moreover, it was possible to propose several ligand exchange reactions and determine their viability (see chapter IV).

The coordination of a bipyridine-based ruthenium complex (photosensitizer, PS) at the surface of preformed RuNPs was studied by DFT calculations using the same Ru 55 NP model as previously described (see section 6.2.1).

Four different [Ru(bpy) 3 ] 2+ type complexes with bipyridine ligands functionalized by carboxylic acid groups (carboxylates to assure the electroneutrality of the system) were considered (figure 5.3).

Roberto González Gómez 307 The chosen photosensitizers were based in three bipyridine ligands connected to a ruthenium metal center [Ru(bpy) 3 ] 2+ . PS1 presents two carboxylates (pending group) mode of functionalization already described. [START_REF] Donnell | Photoacidic and Photobasic Behavior of Transition Metal Compounds with Carboxylic Acid Group(s)[END_REF] This PS1 shows a high-degree of rigidity, thus in the contrary, in PS2 complex carboxylate substituents are located in two different bipyridine entities, making it to be a more flexible and as a pincer type ligand. This was designed in order to facilitate the interaction of the carboxylic groups with the Ru 55 NP.

With the aim to improve the anchoring point mobility of the ligand, two other complexes were built by adding a methylene group as spacers between the bipyridine and the carboxylate function (anchoring point). Thus, PS3 has two acetates in the same bipyridine unit and PS4 has them into two different bipyridines.

In the next sections, the interaction of these photosensitizers with the model Ru 55 NP will be analyzed in order to determine the probable incorporation of these dyes onto preformed RuNPs, aiming to predict the formation of the hybrid nanocatalyst.

Roberto González Gómez 308

Interaction of PS with Ru 55 NP with at Low Surface Coverage

Previous ligand exchange studies were analyzed by a combination of experimental and theoretical tools using as starting point octanoate-stabilized RuNPs. The replacements were examined by using preformed ruthenium nanoparticles stabilized with octanoates as a base.

However, due to technical issues, the analyses with the PS were performed with a Ru 55 NP model covered by ethanoates. The obtained coordinates for the optimized structures are presented in the section appendix F.

It is worth to mention that in the previous computational experiments, the most stable coordination mode of carboxylate entities onto the RuNPs was a carboxylate coordinated in a bridging mode (see chapter II & III). Therefore, it was expected that the photosensitizer will have the same behavior. Thus, preliminary DFT calculations were performed by considering a deprotonated photosensitizer with low crowded ruthenium surface (with two ethanoates), following the methodology described in section 6.2.2 and 6.2.3. The results obtained are presented in figure 5.4 for PS1 and PS2 and in figure 5.5 for PS3 and PS4.

The carboxylates of PS1 interact with the Ru 55 NP by only one oxygen atom for each anchoring group. This coordination mode can derive from the rigidity of the photosensitizer. The total adsorption energy obtained was ca. -77.8 kcal.mol -1 , meaning that each carboxylate provides a stability of ca. 38.9 kcal.mol -1 (see section appendix B.5). When comparing these results with the adsorption energy of ethanoates in similar conditions (ca. -50.6 kcal.mol -1 ) one can assume that, in these conditions, a ligand exchange between preformed RuNPs and PS1 will not be favorable.

With a value of ca. -175.5 kcal.mol -1 , the PS2 displays a higher stabilization energy.

However, in this case, the bipyridine ligands also interact with the surface of the NPs which can explain the better stabilization (figure 5.4). But it is probable that this interaction mode cannot be achieved in a more crowded RuNPs, which is the case in the synthetized nanosystems.

Roberto González Gómez 309 ) are also presented.

The influence of a spacer (CH 2 ) was observed by deposing the PS3 and PS4 onto the same low covered Ru 55 NP, where it was noticed the importance of the photosensitizers pending group mobility.

In the case of PS3, the coordination involves the interaction of one of the two carboxylates in a bridging mode and the second one by an oxygen atom only. These data illustrate the influence of the carboxylate coordination mode, monodentate vs interaction in bridging mode. (figure 5.5), which is quite higher (> 15 kcal.mol -1 ) than the value obtained for PS3 and even more than that of PS1. Thus, with PS4, each pending group provides -53.1 kcal.mol -1 of stability to the Ru 55 NP. This value is ca. 2.5 kcal.mol -1 higher than the adsorption energy of an ethanoic acids in the same Ru 55 NP. However, a deeper investigation of the possible exchange mechanisms should be done in order to safely conclude about an effective ligand exchange between PS4 and carboxylates in preformed RuNPs. It is in particular necessary to assess whether the leaving ethanoates will recombine or not with protons.

Nevertheless, it can be proposed an effective ligand exchange between PS4 and carboxylates in preformed RuNPs, at least when there is a low coverage value. ) are also presented.

As a conclusion, the obtained results evidence that the adsorption of the studied PS on the Ru 55 NP at low ligand coverage is stronger when the PS has CH 2 spacers between the bipyridine motives and the carboxylate function. This can be explained by higher flexibility of such anchoring CHAPTER V DFT Calculations PS onto Ru NP Roberto González Gómez 311 groups. In addition, the ligand exchange reaction could be more favorable when the PS used has anchoring groups in different bipyridine entities (PS4). This can be attributed to the larger angle between the carboxylates thus making the carboxylate pincer more adapted for a connection with the ruthenium surface.

Interaction of PS with Ru 55 NP at Intermediate Surface Coverage

According to the data presented in chapter II, a more trustful model compared to real in synthesized RuNPs in order to evaluate ligand exchange at the surface of NPs could be obtained by using a more crowded Ru 55 NP. To perform so, the adsorption energies of the PS were calculated onto a Ru 55 NP bearing 10 ethanoates.

Three of the four PS were considered for this study. First, PS1 and PS2 due to their similitudes with the experimental available compounds despite their adsorption energies at the Ru 55 NP at low surface coverage were not as high as expected for a positive ligand exchange.

Second, the PS4 was also assessed because the higher adsorption energy value obtained with it in previous section showed it was the best PS for a ligand exchange.

The adsorption energy of two ethanoic moieties can be compared with that of the different PS in order to offer trustworthy trends to predict a possible, one to one, ligand exchange.

Again, it must be underlined that it was compared here, the adsorption energies of carboxylates with dissociative adsorption energies of ethanoic acids, i.e. it was implied to consider that the leaving groups will be ethanoic acids. This is one scenario, that should be completed with other exchange mechanisms.

Using a low covered Ru 55 NP, it was observed that the adsorption energy of two ethanoic moieties was higher than that of ethanoates in almost all the cases, except for the PS2 which was shown to interact with the Ru 55 NP via the aryl part of the bipyridine ligand and the PS4 which presented higher adsorption energy value while only interacting via its carboxylic groups. From the CHAPTER V DFT Calculations PS onto Ru NP Roberto González Gómez 312 obtained results, it appeared that the best conditions for an efficient ligand exchange were with PS4 which bears anchoring points in different bipyridine ligands with CH 2 spacers. spacers does influence the adsorption energy by facilitating the coordination of carboxylates.

These observations suggest that the presence of carboxylates in two different bipyridine ligands is a driving force for increasing the PS affinity with the RuNPs. (figure 5.6 c). ).

The results indicate that the PS adsorption energy is highly affected by the position of their anchoring points on the bipyridine moieties, meaning that the coordination angle is crucial for the CHAPTER V DFT Calculations PS onto Ru NP Roberto González Gómez 314 ligand exchange. It is important to highlight that the PS molecules studied present a high steric hindrance which can influence their coordination. However, given the space generated between the PS and the Ru 55 NP (pincer elongate ligand) this effect is reduced at least with the models used that are preformed nanoparticles stabilized by ethanoates.

As previously mentioned, the adsorption energies of PS1 and PS4 were found higher than that observed for two ethanoic acids in the same conditions of surface coverage. These results led to the conclusion of a possible ligand exchange between ethanoates and PS1 or PS4. However, it is essential to study a ligand exchange by introducing the DFT energies in a reliable reaction profile in order to stablish the thermodynamic variable. Thus, in order to probe the thermodynamic viability of the ligand exchange between ethanoates and PS1 or PS4, two reaction profiles were studied, namely the insertion of PS1, and then of PS4, onto Ru 55 (CH 3 COO) 10 (H) 27 together with the liberation of two ethanoic acids (figure 5.7). The obtained results are described in table 5.2 Roberto González Gómez 315 When considering the other models of carboxylic acid stabilized RuNPs studied (using pentanoic and octanoic acids) they present a higher steric hindrance. Consequently, with such RuNPs a change in the ligand exchange reaction spontaneity may be observed. DFT calculations and experimental data would be required in order to corroborate the reactions viability in these pre-stabilization conditions.,

In the next section, the coordination of the more rigid photosensitizer (PS1) will be analyzed into a ligand exchange reaction using a Ru 55 NP model whose surface composition was previously determined by DFT titration (see section 2.5.2). This model corresponds to a high ratio of surface coverage and is closer to real synthesized RuNPs.

CHAPTER V

DFT Calculations PS onto Ru NP Roberto González Gómez 316

Interaction of PS1 with Ru 55 NP at High Surface Coverage

The ligand exchange strategy can be used to incorporate aryl ligand, like benzoic acid, onto the surface of preformed RuNPs without modifying the metal and the ligand structures, as observed using experimental and theoretical tools. Also, the formation of the desired hybrid catalyst can be performed by following this strategy, as demonstrated by the DFT calculations Specially, when the RuNPs have an intermediate crowded coverage. Moreover, it was observed that the most efficient ligand exchange process can be achieved with a PS4 type of photosensitizer.

Besides, DFT calculations previously showed that the rigid studied photosensitizer PS1 could be adsorbed onto the metal surface, but the process spontaneity was not clear. Therefore, in order to elucidate this last point, a DFT analysis of the reaction of PS1 with a more crowded Ru 55 NP having a similar surface composition as the optimal surface coverage found previously by DFT titration (see section 2.5.2), was performed.

The methodology followed was the same as that described in section 5. ) surface coverage ratio. Even more important, the value observed for PS1 at high surface coverage ratio is higher than that of two ethanoic acids, thus indicating that the ligand exchange is less likely to occur in these conditions.

Nevertheless, these results look inadequate because the coordination mode of PS1 in both Ru 55 (CH 3 COO) 10 (H) 27 and Ru 55 (CH 3 COO) 14 (H) 31 NP models seems to be similar (figure 5.8). Thus, the difference in adsorption energy cannot be easily explained. together with the liberation of two ethanoic acids (table 5.4). Roberto González Gómez 318 As in previous sections, the ligand exchange reaction profile was analyzed by considering a one to one carboxylate exchange meaning that the introduction of PS1 induces the release of two ethanoic acid molecules. In these conditions, it was observed a positive DFT reaction energy. This result indicates that the adsorption of PS1 ligand at the surface of crowded RuNPs stabilized by ethanoates is not feasible by a ligand exchange strategy, again provided that ethanoates recombine with adsorbed hydrides.

However, this data only points out the importance to select the right photosensitizer to favor the ligand exchange. Indeed, PS1 is the most rigid ligand among the series of PS studied in this work. Thus, its adsorption could be expected to not be an easy task, as supported by the DFT calculations. Owing to the better effectiveness observed in the ligand exchange process when studying the adsorption of PS4. It can be assumed that this PS should be the target molecule to build an hybrid nanocatalyst. This reaction is described in scheme 5.1 and will be the object of future work. Anyway, it is worth to point out that the best catalyst to assay, will be the PS4 in an intermediate surface covered RuNPs. Like the one obtained by the system Ru x (C 4 H 9 COOH) 0.30 NPs.

Conclusion

The main target of this PhD work was to generate a base of scientific knowledge in the formation of hybrid nanocatalyst, composed of RuNPs and photosensitizers. A crucial point of this study was to find a proper methodology that allows the grafting of these materials without modifying its own properties. Moreover, the principal aim was to combine their properties to obtain a reliable hybrid nanocatalyst that can be used for the water splitting process.

The combination of experimental and theoretical tools allowed to create a solid base where the structure/properties of the ruthenium nanomaterials could be understood. In the firsts chapters, it was described the formation of RuNPs with different stabilizing agent (ethanoic, pentanoic and octanoic acid) and their characterization. Once the nanosystems properties were described, it was stablished a trustworthy strategy (ligand exchange) to include aryl ligands onto stable, homogeneous and well-dispersed RuNPs without observing a significant modification in its structure. Therefore, this strategy was chosen to build the hybrid nanocatalyst.

In this chapter, four different [Ru(byp) 3 ] 2+ type complexes containing bipyridine ligands modified with carboxylic acid as anchoring groups were designed in order to study their adsorption at the surface of models of RuNPs. These complexes were selected owing to their interest as photosensitizers to harvest light energy and facilitate the electron transfer towards a catalyst for the production of hydrogen by photolysis of water molecules. The main objective of this theoretical study was thus to determine the ability of these complexes to anchor at metal surface in order to determine which of them is the best PS to favor the formation of hybrid nanomaterial with [Ru(byp) 3 ] 2+ -RuNP structure. The chosen strategy for studying the PS adsorption was a ligand exchange reaction. This choice was based on results of previous chapters where it was demonstrated that aryl arboxylic acids can exchange at the surface of RuNPs but only if their CHAPTER V

Conclusion

Roberto González Gómez 320 adsorption energies are appropriate to allow this exchange. This meant that the exchanging ligands had to have an enough difference in terms of adsorption energy to favor the adsorption and release reactions in parallel.

Firstly, the study focused on the determination of PS adsorption onto non-crowded Ru 55 NP surface. It was observed that the bipyridine ligands with a CH 2 spacer between the bipyridine pattern and the anchoring point (carboxylic acid group), are more apt to adsorb at the metal surface. A better adsorption was also observed when the anchoring groups were beard by two different bipyridine ligands. This was attributed to the higher ligand flexibility obtained in these conditions and its ability to act as a pincer ligand given a more appropriate angle for coordination at the RuNPs surface. All observations led to PS4 to be the more appropriate photosensitizer.

Then, the adsorption of the photosensitizers was studied by considering model Ru 55 NPs with an intermediate surface coverage ratio. A spontaneous ligand exchange was observed, mainly with PS1 and PS4 photosensitizers. Moreover, PS4 proved to have best effectivity in the ligand exchange process. From these results we could conclude that the structure of the photosensitizer and the surface coverage ratio of the RuNPs, that is the quantity of capping ligands, are two key-points that influence strongly the viability of the PS adsorption onto RuNPs via a ligand exchange strategy.

From the theoretical studies performed, one can conclude that the anchoring of a photosensitizer onto preformed RuNPs is feasible and, depending upon the experimental conditions, can be thermodynamically spontaneous. However, these are preliminary results that need to be taken with caution due to several other variable that can affect the ligand exchange effectivity, like the nature of the photosensitizers, their steric hindrance, acidity, the NP surface coverage ratio, the exchanged ligand, the possible recombination with protons, etc. Therefore, in order to finish this study and make it more reliable, more calculations are required.

Nevertheless, the presented data indicate that the strategy chosen in order to anchor photosensitizers onto preformed RuNPs is efficient and that the formation of the hybrid [PS]-RuNP nanomaterials is achievable by this way. Lastly, the gathered information points out that the synthesis of the desired hybrid nanocatalysts to be used in the water splitting process, may be easier obtained by using a photosensitizer like PS4 and an intermediate crowded nanoparticle system. Given these conclusions, the RuNPs stabilized by 0.3 equiv. of pentanoic acid may be Roberto González Gómez 321 those to experiment first in an exchange reaction with PS4 in order to get a hybrid nanocatalyst and evaluate its catalytic properties in the photolysis of water for the production of hydrogen.

CHAPTER VI Experimental and

Theoretical DFT

Specifications

Roberto González Gómez 325

6.1 Experimental Part

Generals and Chemical Products

All the operations for the synthesis of ruthenium nanoparticles were carried out using standard Schlenk tubes, Fisher-Porter bottle (Avitec) techniques or in a globe-box (MBRAUN)

under argon atmosphere (Air Liquide, Alphagaz Smartop). The solvents (tetrahydrofuran, toluene and n-pentane) were purchased from Carlo-Erba, dehydrated through filtration on adequate columns in a purification apparatus (MBRAUN) and degassed according to freeze-pump-thaw process just before use. The ruthenium precursor, [Ru(COD)(COT)] (ruthenium-1,5-cyclooctadiene -1,3,5-cyclooctatriene), was synthesized from RuCl 3 ▪xH 2 O (Janssen) by following an established procedure. [START_REF] Porri | A New Synthetic Method for the Preparation of Cyclo-olefin Ruthenium Complexes[END_REF] Glacial ethanoic acid was gathered from Acros Organics and degassed before used by bubbling argon for 30 min. The other liquid carboxylic acids (pentanoic and octanoic acid) were purchased from Sigma-Aldrich, purified by fractional distillation under reduced pressure, degassed under vacuum at the liquid nitrogen temperature by 3 vacuum/argon cycles, dried under molecular sieves and preserved in the globe-box. Benzoic acid (Alfa Aesar) was purified by recrystallization in benzene, [START_REF] Schzab | Preparation of benzoic acid of high purity[END_REF] dried under vacuum overnight and stored in the globe-box.

Hydrogen gas was bought from Air liquid (Alphagaz). Chloroform-d 1 benzene-d 6 , toluene-d 8 and THF-d [START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] for NMR studies were obtained from Euriso-top and stored on activated molecular sieves

Roberto González Gómez 326

The chemical reagents used are enlisted hereafter with indication of the supplier and their purity degree.  Granular zinc (Merck, 95.0 %)

Synthesis Procedures

Synthesis of [Ru(COD)(COT)]

Before starting the [Ru(COD)(COT)] (figure 6.1) synthetic procedure, the 1,5-cyclooctadiene was degassed by bubbling argon for ca. 60 min. Then, 1,5-cyclooctadiene was filtrated using a 5 cm column of previously dried alumina under inert atmosphere. The purified 1,5-cyclooctadiene was stored under argon and kept protected from the light to avoid the formation of reactive peroxides.

Roberto González Gómez 327 Ruthenium-1,5-cyclooctadiene-1,3,5-cyclooctatriene ([Ru(COD)(COT)]) was prepared conforming to a published methodology [START_REF] Porri | A New Synthetic Method for the Preparation of Cyclo-olefin Ruthenium Complexes[END_REF] from RuCl After that, the reaction mixture was cooled down before filtration through a 3 cm column of dried alumina and washings (≤ three times) with 20 mL of degassed toluene. Then, the solution was evaporated to dryness leading to a solid that was extracted with pentane. The obtained solution was filtered on a 5 cm column of dried alumina with successive additions of degassed pentane.

Then, the collected yellow solution was concentrated to 10 mL under high-vacuum before stored overnight in a freezer (ca. -20 °C). The yellow crystals formed were then purified by recrystallization in dried pentane. Finally, the resulting air-sensitive yellow crystals were preserved under argon at -30 °C inside the globe-box. The purity of the sample was confirmed by 1 H-NMR spectroscopy (figure 6.2) in comparison to a reported spectrum.

General Synthesis of Ruthenium Nanoparticles

As a general procedure (scheme 6.1), 30 mg of ruthenium organometallic precursor (0.095 mmol), [Ru(COD)(COT)], were dissolved in 20 mL of a given solvent (pentane or THF) into a Fisher-Porter reactor under vigorous stirring till a yellow homogeneous solution was obtained. The procedure was performed inside the globe-box. After, a solution of a given dried carboxylic acid in the same solvent was added via syringe under argon atmosphere using vacuum line techniques (volatile carboxylic acids) or inside the globe-box (other ligands). After addition of the stabilizing agent, the argon atmosphere was evacuated under high-vacuum and the reactor was pressurized with 3 bar of molecular hydrogen at r.t. In all cases, the initial yellow solution turned black in a few minutes. The gas pressure and the vigorous stirring were maintained for 30 min or overnight. In the first case, the time was split into 10 min of dynamic hydrogen pressure and 20 min of static gas pressure. After this reaction time, a blackish brown suspension was obtained. Finally, the remained hydrogen was evacuated under high-vacuum and the reaction mixture was concentrated for electron microscopy analyses.

Roberto González Gómez 329 The RCOOH/[Ru] ratios (molar equivalents per ruthenium precursor) used are described below (table 6.1).

Microanalysis

Elemental analyses (EA) were performed by Isabelle Borget in the "Service d´Analyses

Chimiques" at the LCC-CNRS for carbon and hydrogen concentration determinations.

The metal content in the nanoparticles was obtained by Alain Moreau in the same facilities by using a ICAP 76001ICP-AES Analyser of ThemoScientific equipment.

Vibrational Spectroscopy

Ruthenium nanoparticles vibrational properties were obtained by attenuated total reflectance infrared (ATR-FTIR) and simple Fourier-transform infrared (FTIR). The spectra were recorded under inert atmosphere in a Perkin-Elmer GX2000 spectrometer installed inside a globe-box at the range of [400 -4000 cm -1 ]. FTIR spectra were obtained in the same conditions as ATR-FTIR but with potassium bromide (KBr) as support and diluent.

CHAPTER VI Experimental Part

Roberto González Gómez 332

Gas Chromatography

The quantity of reactive hydrogen atoms present at the RuNPs surface was obtained by gas chromatography (GC). The analyses were performed with a Hewlett Packard HP-5890 Series II instrument equipped with a flame ionization detector and a 30 m non-polar 100.0 % capillary column (0.32 mm diameter, 0.25 mm film thickness) of dimethyl polysiloxane (SGE PB1), using helium (2 mL.min -1 ) as carried gas.

Methodology for surface reactive hydrogen atoms: The temperature of the injector and detector was set at 250 °C and that of the column at 60 °C. The initial stabilization time was 3 min and then, a temperature ramp was set from 60 to 170 °C (15 °C.min -1 ), three extra minutes were left as final program time.

Wide-Angle X-Ray Scattering

Wide-angle X-ray scattering (WAXS) measurements were performed at CEMES-CNRS by Pierre Lecante. Small amounts of purified RuNPs were put in 1.0 or 0.5 mm diameter Lindermann glass capillaries under inert atmosphere and then sealed. The samples were irradiated with graphite-monochromatized molybdenum k (0.071069 nm) radiation and the X-ray scattering intensity measurements were performed using a dedicated two-axis diffractometer. Time for the data collection was typically 20 h for a set of 457 measurements collected at r.t. in the range of and a gradient pulse length () among [2.0 -3.0 m]. The peak integration decay curves of the DOSY spectra were fitted according to the Stejskal-Tanner function. [START_REF] Connell | Improving the accuracy of pulsed field gradient NMR diffusion experiments: Correction for gradient non-uniformity[END_REF] 𝑆

(𝐺) = 𝑆 0 𝑒 [-𝐷𝛾 2 𝐺 2 𝛿 2 ∆ ′ ]
Where S and S 0 are the signal amplitude in presence and absence of diffusion, D is the diffusion coefficient of the moiety, γ is a linear combination of the gyromagnetic ratios, δ is the time where the pulse was switched on, G is the gradient amplitude and Δ' is the diffusion delay time corrected of the diffusions effects during the gradient pulse.

NOESY measurements were performed with delay time of 2.0 s and the mixing time was set to 100.0 ms. These studies were done with the aim to find the exchange-transferred nuclear Overhauser effect (et-NOE) sign. This variable depends mainly on the correlation time (τ c ) which relies on the molecular weight of the solubilized moieties. [START_REF] Post | Exchange-transferred NOE spectroscopy and bound ligand structure determination[END_REF] Typically, small molecules (MW < 600) displays positive et-NOES, medium size moieties (600 < MW < 1200) exhibit et-NOE close to zero, if this case is presented a rotating-frame Overhauser spectroscopy (ROESY) NMR experiment should be performed. Finally, big species as the MNPs present a negative et-NOE (Figure 6.3).

Roberto González Gómez 334 [274]

Calculation of Hydrodynamic Radius

Hydrodynamic radii (r H ) were estimated from the diffusion coefficients measured in 2D

DOSY experiments [START_REF] Canzi | Diffusion-Ordered NMR Spectroscopy as a Reliable Alternative to TEM for Determining the Size of Gold Nanoparticles in Organic Solutions[END_REF] performed in benzene-d [START_REF] Tovar | Light-driven water oxidation using hybrid photosensitizer-decorated Co 3 O 4 nanoparticles[END_REF] or THF-d 8 by following the Stokes-Einstein law for spherical particles diffusion in solution. ([303], [START_REF] Fiurasek | Phosphonic and Sulfonic Acid-Functionalized Gold Nanoparticles: A Solid-State NMR Study[END_REF]) 𝐷 = 𝑘 𝐵 𝑇 6𝜋𝜂𝑟 𝐻 Temperature (T) and viscosity (η) are the principal variables to consider for the hydrodynamic radius calculation, which are intrinsically related. Benzene-d 6 viscosity value has a higher dependence with the temperature than THF-d 8 (table 6.

Roberto González Gómez 335

The hydrodynamic radii were related with the RuNPs mean sizes obtained by TEM studies according to the next mathematical relation gathered from the literature. [START_REF] Zheng | A simple and fast method to study the hydrodynamic size difference of protein disulfide isomerase in oxidized and reduced form using gold nanoparticles and dynamic light scattering[END_REF] 𝑟 𝐻 = 𝐷 𝑅𝑢𝑁𝑃 2 + 𝐷 𝐻(𝐿𝑖𝑔𝑎𝑛𝑑)

Quantification of Ligand Surface Coverage

The quantifications of ligand surface coverage were performed from DOSY 1 H-NMR spectra, according to a published methodology. [START_REF] Coppel | Full Characterization of Colloidal Solutions of Long-Alkyl-Chain-Amine-Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State, Equilibria, and Affinity[END_REF] From the integration (I [0] ) of the resonances of a specific region (ligand chemical shift) in the 1D DOSY 1 H-NMR spectra, the relative amounts (X) of ligands either strongly attached (X Is ) and weakly bonded or in exchange (X Iw + X If ) were obtained.

Then, considering the observed diffusion coefficients as the weighted average of the surface-linked (D Is ), exchanging ligand (D Iw ) and free ligand (D If ) measured, the quantification of different types of ligand surrounding the RuNPs were calculated by following the next equations. The surface coverage value per ruthenium surface atoms (I s,w,f /Ru surf ) and the quantity of ligand interacting per ruthenium nanoparticles (I s,w,f /Ru NP ) were obtained by using the RuNPs mean size obtained by TEM, the crystalline close pack (WAXS and HRTEM) and the magic number for metal clusters according to the next equations. Roberto González Gómez 336

RuNPs Surface Saturation

NOESY 1 H-NMR allowed to get information on the surface saturation of the RuNPs. 2D

NOESY experiments permit to observe the presence of negative NOE cross-peaks in the chemical shifts assigned for the ligands. These negative NOE signals are observed when a fast exchange between the weakly interacting (I w ) and exchanging ligand (I f ) is predominating, meaning the confirmation of free ligand present in the deuterated solvent.

Ligand Exchange Quantification

Quantifications of the ligand exchange between different carboxylic acids at RuNPs surface were performed by carrying out a serial of 1 H and DOSY NMR experiments with spectra deconvolution. The quantity of a given ligand present at the RuNPs surface in each step of the ligand exchange was calculated according to the equations described in the section 6.

NOESY NMR studies as described in section 6.1.3.6.3, allowed to determine the interaction of the entering ligand as well as to detect the ligand released after the exchange.

Solid-State Nuclear Magnetic Resonance

Solid-state NMR analyses were performed by Yannick Coppel on a Bruker Avance 400WB spectrometer in the "Service de Resonance Magnétique Nucléaire" at the LCC-CNRS, Toulouse, France. Preparation of the samples was carried out under argon inside a globe-box. The powder of RuNPs was dispersed on porous silica gel (60 Å) by impregnation from a THF NPs colloidal suspension, followed by slow solvent evacuation before filling a 3.2 mm probe ZrO 2 rotor.

Experiments were conducted at a spinning speed of ca. 12 kHz using a 13 C spin -Echo and CPMG pulse sequence.

CHAPTER VI Experimental Part

Roberto González Gómez 337

Heteronuclear correlation spectroscopy (HETCOR) NMR experiments were performed in order to describe the proton-carbon ( 1 H-13 C) correlation at the surface of the RuNPs. Specially, the vicinity of the [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] CO deposited on preformed RuNPs stabilized by carboxylic acids.

Surface Reactivity Studies and Catalysis

Quantification of Surface Reactive Hydrogen Atoms

The quantification of hydrogen attached onto the ruthenium nanoparticles surface was carried out by GC analyses. The RuNPs were dissolved in THF inside a Schlenk reactor to form a homogeneous stable colloidal solution under inert conditions. Then, 10.0 equiv. of olefin (2-norbornene) were added to the reaction mixture and maintained under vigorous stirring at r.t.

during 72 h, the procedure was done according to a previously published methodology. [START_REF] García-Antón | Reactions of olefins with ruthenium hydride nanoparticles: NMR characterization, hydride titration, and room-temperature[END_REF] The solution was filtrated with silica/celite plugs and the resulting samples were taken for estimation of the norbornene conversion into norbornane by GC analyses. The measurements of the amount of alkane formed allowed to determine the necessary quantity of hydrogen atoms for reducing the alkene, and further to calculate the reactive hydrogen per ruthenium surface atom (H reac /Ru surf ) considering the nanoparticle mean size obtained by TEM, the crystalline structure (HRTEM and WAXS) and the magic number theory for metal clusters.

The calculation of surface reactive hydrogen atoms per ruthenium surface atom at r.t. was obtained by applying the next equations.

𝑁 = ( 𝑁𝑃 𝑑 2𝑏(𝑅𝑢 𝑟 ) ) 3 𝑁 = 1 3 (10𝑛 3 -15𝑛 2 + 1𝑛 -3) 𝑁 𝑠𝑢𝑟𝑓 = 10𝑛 2 -20𝑛 + 12 𝑛 𝐻 = 2(𝑛 𝑜𝑙𝑒𝑜𝑓𝑖𝑛 )(% 𝐶𝑜𝑛𝑣 ) 𝐻 𝑟𝑒𝑎𝑐 /𝑅𝑢 𝑠𝑢𝑟𝑓 = ( 𝑛 𝐻 𝑛 𝑅𝑢 ) ( 𝑁 𝑠𝑢𝑟𝑓 𝑁 )
Roberto González Gómez 338 In the first equation, N is the total number of ruthenium atoms per nanoparticle and b is the crystalline closed pack parameter. [START_REF] Hosseini-Monfared | Dioxygen oxidation of 1-phenylethanol with gold nanoparticles and N-hydroxyphthalimide in ionic liquid[END_REF] For the second mathematical statement, n is the number of shells according to the magic number for metal clusters. In the third equation, N surf is the number of ruthenium surface atoms per nanoparticle. [START_REF] Teo | Magic Numbers in Polygonal and Polyhedral Clusters[END_REF] The quantity of reactive hydrogen was obtained with the fourth equation, where % Conv is the 2-norbornene hydrogenation percentage. Finally, the number of hydrides per ruthenium surface atom was obtained with the last relation.

Surface Mapping with 13 CO

The reaction of [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] CO with ruthenium-based nanoparticles was performed in the solid-state, following a previously described procedure. [START_REF] Martínez-Prieto | Zwitterionic amidinates as effective ligands for platinum nanoparticle hydrogenation catalysts[END_REF] A powder of RuNPs was introduced into a small Fisher-Porter reactor (ca. 5 mL) under inert conditions. After, the reactor was evacuated and then pressurized with 1 bar of [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] CO under vigorous stirring. The reaction time was fixed to 15 h. Then, the remaining [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] CO was evacuated by high-vacuum and then the RuNPs sample was analyzed by solid-state NMR.

DFT Calculations

Ru 55 Nanoparticle Model

An ultra-small ca. ). [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] Roberto González Gómez 339 This Ru 55 NP model has a cubo-octahedral full-shell organization ([13], [START_REF] Radi | Nanoscale shape and size control of cubic, cuboctahedral, and octahedral Cu-Cu2O core-shell nanoparticles on Si (100) by one-step, templateless, capping-agent-free electrodeposition[END_REF]) which possesses an overall spherical morphology. The originally designed RuNP has a hcp structure with twelve (101) and two (001) planes, that was shaped in order to establish structural modifications close to the experimental surface heterogeneity. Therefore, the resulting Ru 55 hcp model is not a perfect crystalline structure.

Firstly, an adatom was introduced with the purpose to generate a B 4 and a B 5 sites. A slightly corrugated facet was also obtained by removing an atom line between two (101) planes (figure 6.5). The surface area of the chosen DFT-PBE optimized Ru 55 nanoparticle, which possess 11 ruthenium atoms in the core and 44 at the surface, is 258 Å 2 , this value is ca. 25 Å 2 less than a perfect spherical 1.0 nm particle. [START_REF] Sokolov | Are Nanoparticles Spherical or Quasi-Spherical?[END_REF] Roberto González Gómez 340 [82]

Periodic DFT Calculations of Ru 55 Nanoparticles

Spin polarized density functional theory (DFT) calculations were performed using the Vienna ab initio simulation package (VASP) software, ([313], [START_REF] Bignozzi | Simple poly (pyridine) ruthenium (II) photosensitizer:(2, 2'-bipyridine) tetracyanoruthenate (II)[END_REF]) that is a periodic-first principles software that uses the projector augmented wave (PAW) method to describe the electron-core interaction in atoms and a plane wave basis set. ([315], [START_REF] Ponder | Surface chemistry and electrochemistry of supported zerovalent iron nanoparticles in the remediation of aqueous metal contaminants[END_REF]) The software has been widely used to describe liquids, metals, nanostructures, semiconductors and insulators, and general surfaces. [START_REF] Hafner | Ab-initio simulations of materials using VASP: Density-functional theory and beyond[END_REF] The resolution of the Schrödinger equation for metal systems is quite efficient by using this methodology, specially due to the usually HOMO-LUMO degeneracy which is a common phenomenon found for the iterative resolution of the Schrödinger equation in these systems.

Calculations were performed with the PBE functional developed by Perdew, Burke, and Ernzerhof (PBE), [START_REF] Perdew | Generalized Gradient Approximation Made Simple[END_REF] which is a conventional functional among the generalized gradient approximation (GGA) functionals that is widely used in surface science. [START_REF] Hammer | Theoretical Surface Science and Catalysis-Calculations and Concepts[END_REF] Projector augmented waves (PAW) potentials were utilized with kinetic energy cutoff of 500 eV. PAW data sets for metal atom treating ns, (n-1)p and (n-1)d states (14 e -for ruthenium). -centered [START_REF] Monkhorst | Special points for Brillouin-zone integrations[END_REF] Frequency calculations were performed at the same level of theory. Finite differences are used to calculate the Hessian matrix. In other words, each ion is displaced in every direction by a small positive and negative displacement. The selective dynamics method available in VASP allows the calculation of vibrational normal modes of a subset of atoms by computing frequencies within atoms far away from an adsorption or a catalytic site (reducing the use of computational resources).

CHAPTER VI DFT Calculations

Roberto González Gómez 342

Ligand Adsorption Energies Calculations

The adsorption energies of a given ligand (∆𝐸 𝑎𝑑𝑠 𝐿 𝑖 ) were obtained through first principles DFT studies by consider the adsorption of n ligands (L i ) at the surface of the Ru 55 NP. The calculation of the average adsorption energy requires to fully optimize the free ligand, the reference NP and its counterpart stabilized with the n ligands (L). Thus, the adsorption energy was calculated as follows.

∆𝐸 𝑎𝑑𝑠 𝐿 𝑖 = 1 𝑛 (𝐸 𝑅𝑢 55 (𝐿 𝑖 ) 𝑛 -𝐸 𝑅𝑢 55 -𝑛𝐸 𝐿 𝑖 )
Where the obtained energy (E) are represented by the DFT-PBE energies of the molecules at 0 K, without taking into account zero-point energy and thermal corrections.

Regarding the coordination modes, there is some arbitrariness in the recognition of a chemical bond. But criteria are needed in order to define the possible bridging (μ n ) character and hapticity (η m ) between surface ligands and the Ru 55 NP. Thus, it was considered that a bond exists between a metal atom (Ru) and a ligand atom when the distance between them was less than 2.1 Å for H, 2.5 Å for C, 2.5 Å for N, 2.5 Å for O and 3.5 Å for F.

Reaction Barriers

The reaction barriers of single step reactions were calculated by exploring with a nudged elastic band method the minimum energy pathway (MEP) between two stable states of the reactants and the products. The method consists in the optimization of a set of interpolated structures between R and P. Each optimized point on the path is an energy minimum in all directions perpendicular to the path and there is a highest energy lying structure which is the transition state.

The climbing image nudge elastic band method (CINEB) ([319], [START_REF] Connell | Improving the accuracy of pulsed field gradient NMR diffusion experiments: Correction for gradient non-uniformity[END_REF]) has been used with a spring force between images of 5 eV and a tolerance force of 0.02 eV/Å. The harmonic vibrational Roberto González Gómez 343 frequencies were systematically calculated in order to distinguish minima and saddle points by using the dynamical matrix code implement in VASP, as well as the VASPTST tool. [START_REF] Adamo | Optimization methods for finding minimum energy paths Optimization methods for finding minimum energy paths[END_REF]

NMR Calculations of Organic Moieties on Small Ruthenium Clusters

The calculation of half-integer spin NMR properties with the gauge including projected augmented wave (GIPAW) method is available with VASP. [START_REF] Pickard | All-electron magnetic response with pseudopotentials: NMR chemical shifts[END_REF] However, the methodology for metal-type electronic structures is not currently available. [START_REF] Marzari | Spin and orbital magnetic response in metals: Susceptibility and NMR shifts[END_REF] Thus, all NMR calculations were done on small [Ru 6 ] clusters by using the Gaussian09 software (taking advantage that NMR chemical shieldings are local properties). [START_REF] Frisch | Gaussian 09 Revison D.01[END_REF] Pseudopotentials and basis sets for [Ru 6 ] clusters were obtained from a previous published procedure (basis set I). [START_REF] Del Rosal | Ligand effect on the NMR , vibrational and structural properties of tetra-and hexanuclear ruthenium hydrido clusters : a theoretical investigation[END_REF] It was used the Stuttgart-Dresden relativistic effective core potential (SDD-ECP) and its basis set developed for ruthenium-augmented core with an f-polarization

function (ζ f = 1.235
). [START_REF] Dolg | Energy-adjusted abinitio pseudopotentials for the first row transition elements[END_REF] The SDD-ECP and is basis were also used for carbon, oxygen and fluorine augmented with a set of d-polarization functions (C: ξ d = 0.587, O: ξ d = 0.961, F: ξ d = 1.577). [START_REF] Bergner | Ab initio energy-adjusted pseudopotentials for elements of groups 13-17[END_REF] Hydrogen atoms were treated with the polarized double-zeta quality 6-31G(d,p) basis set. ([327], [START_REF] Radi | Nanoscale shape and size control of cubic, cuboctahedral, and octahedral Cu-Cu2O core-shell nanoparticles on Si (100) by one-step, templateless, capping-agent-free electrodeposition[END_REF])

The correlation-consistent polarized valence triple zeta (cc-pvtz) basis set was considered for ethanoic acid and ethanoate (basis set II). 1 H and [START_REF] Schmid | Nanoparticles: From Theory to Applications[END_REF] C chemical shifts of ethanoic acid were similar with both basis set (I and II), but there was a higher dependence for the ethanoate.

The chemical shieldings were calculated on fully optimized structures without any geometry constraints at the DFT-PBE0 level of theory, where PBE0 is a hybrid functional, [START_REF] Adamo | Toward reliable density functional methods without adjustable parameters: The PBE0 model[END_REF] and gauge Including Atomic Orbital method (GIAO). ([345]- [START_REF] Wolinski | Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations[END_REF]) The reliability of this computational strategy has already been proven in several applications. ([166], [START_REF] Martínez-Prieto | Zwitterionic amidinates as effective ligands for platinum nanoparticle hydrogenation catalysts[END_REF])

Theoretical chemical shifts can be obtained by computing isotropic chemical shieldings (σ)

for both the investigated compounds and the reference (TMS) at the same level of theory, as it is described hereafter.

Roberto González Gómez 344

𝛿 𝑖 = (𝜎 𝑅𝑒𝑓 -𝜎 𝑖 )(10 6 )
Where σ is calculated in ppm.

Two different TMS chemicals shielding (σ ref ) were used to calculate the chemical shift (δ) from the isotropic shielding constants (σ i ). [START_REF] Lodewyk | Computational Prediction of 1H and 13C Chemical Shifts: A Useful Tool for Natural Product, Mechanistic, and Synthetic Organic Chemistry[END_REF] The cc-pvdz basis set: σ H-TMS = 31.66 and σ C-TMS = 196.81 ppm and the cc-pvtz basis set: σ H-TMS = 31.57 and σ C-TMS = 189.16 ppm. ([336], [START_REF] Pickard | All-electron magnetic response with pseudopotentials: NMR chemical shifts[END_REF])

Ab initio Thermodynamics

The energies obtained by ab initio calculations were implicitly obtained in vacuum (p = 0 Pa) and without any thermal nor zero-point energies (ZPE, T = 0 K). Nevertheless, it is possible to describe, analyze or even predict thermodynamic properties such as Gibbs free energies (Δ a G°) by combining first principles calculations and a thermodynamic based methodology, ([338], [START_REF] Frisch | Gaussian 09 Revison D.01[END_REF]) which is the base of the ab initio thermodynamics method.

Phase diagrams were obtained by using this methodology, as shown in section 2.5.2, where the standard Gibbs free energies of adsorption of the most stable structures, at certain fixed temperature, as a function of concentration and pressure were plotted. Layouts were conceived when the interacting moieties (ligands) -carboxylic acid (R-COOH) solution (THF) and hydrogen pressure (H 2 ) -were found in the equilibrium. As well, phase diagrams were obtained by looking at the relationship of the ligands with THF at the equilibrium.

As an example, the co-adsorption of two species at the surface of Ru 55 NP (liquid and gas phases):

L 1 (R-COOH) & L 2 (H 2 )
. Such process is the starting point of the Langmuir-Hinshelwood mechanism in heterogeneous catalysis. ([340], [START_REF] Bergner | Ab initio energy-adjusted pseudopotentials for elements of groups 13-17[END_REF]) The general ligand adsorption reaction onto the Ru 55 NP and the Gibbs free energy (Δ a G°(T,[L 1 ],𝑝 𝐿 2 )) calculations are briefly presented hereafter.

𝑅𝑢𝑁𝑃 + 𝑛 1 𝐿 1 + 𝑛 2 𝐿 2 = 𝑛 1 𝐿 1 * + 𝑛 2 𝐿 2 *
The adsorption energy can be calculated as:

∆ 𝑎 𝐸 = 𝐸(𝑛 1 𝐿 1 * , 𝑛 2 𝐿 2 * ) -𝐸(𝑅𝑢𝑁𝑃) -𝑛 1 𝐸(𝐿 1 ) -𝑛 2 𝐸(𝐿 2 )
For Δ a G° calculations, the two co-adsorbed species (L 1 & L 2 ) are considered in thermodynamic equilibrium with the metal NP, as follows:

Roberto González Gómez 345

∆ 𝑎 𝐺 = [∆𝐺 °-𝑛 1 𝜇(𝐿 1 , 𝑇, 𝑐) -𝑛 2 𝜇(𝐿 2 ,

𝑇, 𝑝)] 𝐴

Where A is the surface area of the optimized Ru 55 NP (258 Å 2 ). Thus, the standard Gibbs free energies (ΔG°) can be obtained from the next equation.

∆𝐺 °= 𝐸(𝑛 1 𝐿 1 * , 𝑛 2 𝐿 2 * ) -𝐸(𝑅𝑢𝑁𝑃) + 𝐹 𝑣𝑖𝑏 (𝑛 1 𝐿 1 * ) + 𝐹 𝑣𝑖𝑏 (𝑛 2 𝐿 2 * )
F vib stand for the vibrational contributions to the standard Gibbs free energy of the metal lattice. These do not appear in this last equation, because it has been considered identical between the reference Ru 55 NP and the ligand-stabilized Ru 55 NP. This approximation avoids the expensive calculation of metal-metal normal modes of vibrations.

As the surrounding medium acts as a reservoir of ligands (L i ), the chemical potentials (μ)

were calculated from the standard chemical potential and the activity of the ligand, as follows:

𝜇(𝐿 𝑖 , 𝑇, 𝑝) = 𝜇 ᶱ (𝐿 𝑖 , 𝑇, 𝑝 °) + 𝑘𝑇 ln 𝑎 (𝐿 𝑖 )

The standard chemical potentials (μᶱ(L i , T, p)) were obtained from a previous mathematical statement report, where the standard enthalpy (H T °(L i )) and entropy (S T °(L i )) were calculated from the L partition function, as it is described hereafter. [START_REF] Mcquarrie | Statistical Mechanics[END_REF] 𝜇 ᶱ (𝐿 𝑖 , 𝑇, 𝑝 °) = 𝐸 𝐷𝐹𝑇 (𝐿 𝑖 ) + 𝐻 𝑇 °(𝐿 𝑖 ) -𝑇𝑆 𝑇 °(𝐿 𝑖 )

Surface adsorption Gibbs free energies (Δ a G) can be plotted as a function of two chemical potentials μ(L 1 ) and μ(L 2 ) for several surface compositions (n 1 & n 2 ). As a consequence, reasonable thermodynamically stable geometries are highlighted on surface phase diagrams in the [μ(L 1 ), μ(L 2 )] ranges.

Standard enthalpy (H T °(R-COOH, g)) and entropy (S T °(R-COOH, g)) were obtained with the Gaussian09 software, THF was taken into account as a solvent thanks to the solvation model density (SMD) [START_REF] Marenich | Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions[END_REF] variation of the integral equation formalism of the polarizable continuum model (IEFPCM). [START_REF] Tomasi | Quantum mechanical continuum solvation models[END_REF] While, standard enthalpy (H T °(H 2 , g)) and entropy (S T °(H 2 , g)) were taken from the JANAF tables. [START_REF] Chase | JANAF Thermochemical Tables[END_REF] The chemical potential for H was obtained as ½ μ(H 2 , T, p), since the dissociative adsorption is the one that is considered. Free energy thermodynamic diagrams were produced with the home-made aithermo program. [START_REF] Cusinato | Shape, electronic structure and steric effects of organometallic nanocatalysts: relevant tools to improve the synergy between theory and experiment[END_REF] The ab initio thermodynamics analyses were performed in the range of [ The charge spilling, a criterion that assesses the quality of the projection, was systematically lower than 0.7 %. Atomic charges were provided both by integrating the pDOS up to the Fermi energy and by carrying out the atoms-in-molecules (AIM) analysis of the charge density. [START_REF] Bader | Atoms in Molecules: A Quantum Theory[END_REF] This methodology is the Mulliken population analysis (MPA) performed with an orthonormal basis set. Since it first starts with a projection of the wavefunction from a planewave basis set to a local basis set, such charges are called pMPA atomic charges. It has recently been

shown that, in the case of non-covalent graphene doping, pMPA charges and natural populations (NPA) [START_REF] Reed | Natural population analysis[END_REF] are rather similar. [START_REF] Gerber | Critical assessment of charge transfer estimates in non-covalent graphene doping[END_REF]

Qualitative Average Bond Strength

The qualitative average bond strengths were obtained for a given A-B bond by integrating up to the Fermi energy the pCOHP values calculated between all valence μ and ν AOs that belong to A and B atoms, the values were obtained as follows:

𝐼𝑝𝐶𝑂𝐻𝑃(𝐴 -𝐵) = ∑ ∑ ∫ 𝑝𝐶𝑂𝐻𝑃 𝜇𝜈 𝐸 𝐹 𝐸 𝑚𝑖𝑛 𝜈∈𝐵 𝜇∈𝐴 (𝜀)𝑑𝜀
Such one-electron derived index must not be considered as a bond dissociation energy (BDE), but it gives a valuable bond strength index which variation follows BDE variations or any property related to bond strength, such as A-B stretching frequencies. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF]

Gibbs Free Energy for HER Reaction

The Gibbs free energy of the adsorbed hydrogen state (ΔG H* ) in the most stables optimized Ru 55 NP structures was obtained by adding the zero-point energy (ΔE ZPE ) and subtracting the enthalpic term (TΔS H ) from the hydrogen adsorption energy on a given optimized structure. It was considered that this value was 5.5 kcal.mol -1 , as reported in a previous published work. [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] The Roberto González Gómez 348 Gibbs free energy for an hydrogen adsorption (ΔG H* ) was obtained with the next mathematical statement.

∆𝐺 𝐻 * = 𝐸(𝐻 * ) -𝐸(𝑠𝑢𝑟𝑓) -1 2 𝐸(𝐻 2 ) + ∆𝐸 𝑍𝑃𝐸 -𝑇∆𝑆 𝐻

GENERAL CONCLUSION

Nowadays, the water splitting process is not a viable methodology for the production of energy due to several issues, like the cost and efficiency. Thus, in order to increase the effectiveness of the process, an efficient photocatalyst needs to be designed. Several new materials have been synthetized to be used in the water splitting process. However, their functionality is not well described. Moreover, a good catalyst that can overcome with the presented water splitting issues has not be found. Therefore, a well-understanding of the photophysical and catalytic properties of these materials is crucial to design a suitable catalyst, that can be used for the photoproduction of hydrogen from water.

The aim of this PhD work was contributing to the improvement of hydrogen (H 2 ) production using solar power. Hence, our efforts were focused in the separation of water using light in order to obtain the desired energy source. This work provides a solid scientific base that gives some insights about the proper design of a reliable catalyst for the water splitting process.

This doctorate thesis was an upstream study in the large context of hydrogen production by photolysis of water molecules. The main objective was to determine the appropriateness of a family of ruthenium-based nanomaterials as catalysts for the hydrogen evolution reaction (HER), which is the second reaction involved in the water splitting process, where ruthenium has known a renewed attention these last years.

For that purpose, the PhD work was centered on the synthesis of model ruthenium nanoparticles (RuNPs) using carboxylic acids as stabilizing agents and their full characterization by means of different tools including theoretical studies. A second objective was to evaluate the potential of the obtained nanoparticles in the HER reaction. The final aim was the design of hybrid nanomaterials based on the association of RuNPs and a photosensitizer derived from the [Ru(bipy) 3 ] 2+ complex for their evaluation in photocatalytic conditions.

In the first chapter of this PhD manuscript is based on an experimental and a theoretical background based on the synthesis, stability, and catalytic activity of RuNPs. In the second chapter, it was described the synthesis of RuNPs by following the organometallic approach and using ethanoic acid as a stabilizer. A synthesis optimization and a full characterization of the obtained nanoparticles were performed. By this way, it was obtained a homogenous population of small and well-dispersed ethanoic acid stabilized RuNPs of ca. 1.5 nm, the composition of which was precisely determined in particular by deep NMR analyses.

Then, the characterization data were taken as a starting point to build a trustworthy theoretical model able to explain the surface and electronic properties of these RuNPs. First, it was determined that the ethanoic acid interacts with the metal surface as a carboxylate. Then, it was possible to define a precise mapping of the RuNPs surface, both in terms of nature of surface species (stabilizer and hydrides) and of their quantity, thanks to a good agreement between experimental and theoretical data. It is worth to note that the quantity of hydrides was low compared to previous systems of RuNPs.

The findings allowed to corroborate the reliability of the theoretical model used and to evidence its interest in order to get trustful trends for a better understanding of the ligand influence on the RuNPs properties. The theoretical model also allowed achieving reliable trends in order to predict the catalytic viability of the RuNPs regarding the hydrogen evolution reaction (HER), thus evidencing the need to find a good compromise between stability and reactivity

Chapter III was focused on the use of carboxylic acids with longer alkyl chains to stabilize RuNPs, namely pentanoic and octanoic acids. This choice was made aiming to study the influence of the alkyl chain length of carboxylic acids on the surface properties of the particles. More homogeneous and well-defined particles were formed with these carboxylic acids. Moreover, optimization of the synthesis conditions allowed to get particles of similar size as with ethanoic acid. Thus, a comparison of the RuNPs surface composition and properties was performed in order to rationalize the influence of the stabilizer.

General Conclusion

Roberto González Gómez 351

As previously observed with ethanoic acid, experimental and theoretical results were in good accordance towards the coordination of the pentanoic and octanoic acid to be under the carboxylate form and the quantity of co-adsorbed hydrides to be low. Comparative studies highlighted the direct influence of the alkyl part of the stabilizing ligand. In fact, longer the alkyl chain, lower is the necessary quantity of ligand to stabilize RuNPs of similar mean sizes.

Theoretical evaluation of the systems of RuNPs for the HER reaction led to the conclusion that among the carboxylic acid stabilized RuNPs analyzed, the particles with a moderate surface coverage by a carboxylate ligand not too long is probably the best compromise in terms of catalytic activity, presenting an hydrogen adsorption energy close to that of platinum which is presently the best catalyst for the HER reaction. From these results it appeared that the most appropriate nanomaterial is the RuNPs stabilized by 0.3 equiv. of pentanoic. Preliminary catalytic tests tend to indicate that this nanomaterial is able to catalyze the HER reaction but more experiments are needed before being able to judge on its real potential.

Once the properties of the RuNPs stabilized by carboxylic acids were determined, the next logical step was to build the hybrid material. However, it was noticed that the reduction of aryl ligands could occur in the presence of RuNPs. Therefore, a one-step synthesis to form the hybrid material was not possible due to the risk of changing the photonic properties of the bipyridine based photosensitizers. Thus, chapter IV is dedicated to ligand exchange reactions at the surface of carboxylic acid stabilized RuNPs, which was the strategy chosen to avoid this issue.

Thus, these studies were performed in order to determine the appropriate conditions to perform an exchange of ligands at the ruthenium surface, the final aim being to exchange a photosensitizer bearing carboxylic groups with preformed RuNPs and thus get a hybrid [PS]-RuNP nanomaterial for photocatalysis studies.

Even if the efficiency of the exchange process was not so high, the results demonstrated that it is possible to exchange a carboxylic acid by another one (benzoic or TFA) at RuNP surface.

However, it is necessary to take into account parameters like the acidity and steric hindrance. In particular, it was shown that octanoic acid can be exchanged by benzoic acid. These results are encouraging enough to follow the same way to graft a photosensitizing molecule at the surface of preformed RuNPs through the use of carboxylic acid as anchoring groups.

General Conclusion

Roberto González Gómez 352 In the last chapter of this manuscript, a theoretical study was performed in order to anticipate the grafting of a photosensitizer at the surface of preformed RuNPs stabilized by ethanoates. For this purpose, well-known complexes in HER catalysis was chosen as starting point, namely [Ru(bipy) 3 ] 2+ based compounds. Four different [Ru(bipy) 3 ] 2+ complexes with carboxylic groups on bipyridine ligands at different locations were modelized in order to evaluate their coordination at the metal surface. The results showed that anchoring a carboxylic acid modified [Ru(bipy) 3 ] 2+ complex at the surface of preformed RuNPs is plausible by substituting initial ligands (ethanoates). One important parameter for such a grafting appeared to be the presence of carboxylic acid functions onto two different bipyridine ligands of the complex, the angle obtained in these conditions seeming favorable for the coordination. However, these results are preliminary and need to be completed. The next step will be to test experimentally the anchoring and when the hybrid nanomaterial will be obtained to evaluate its catalytic properties in the HER.

Beside the novelty of the ligands used for the synthesis of ruthenium nanoparticles, the major contribution of this PhD work is the development in parallel of experimental and theoretical approaches in order to bring a better understanding of the structure/properties relationships at the nanoscale of RuNPs stabilized by carboxylic acids. The results obtained reinforce the interest of doing so to characterize better or anticipate the behavior of metal nanoparticles.

The catalytic reaction envisaged for the application of the studied nanomaterials was the water splitting process that allows hydrogen production. Unfortunately, only preliminary theoretical results on synthetizing the catalyst were obtained and the results obtained, even if they are encouraging, need to be confirmed before fully describing them and later on, teste them.

As a final statement, the results obtained during this PhD will be very useful in the future to continue the development of this research. The tools developed can be applied in order to improve other nanocatalysts for the same target reaction or for other catalytic transformations.

RESUME DE LA THESE

La mise au point de modes de production d'énergies renouvelables figure parmi les grands défis actuels de notre société en raison de l'augmentation continue des gaz polluants provenant de l'utilisation de combustibles fossiles et de la demande croissante en énergie.

Si l'énergie solaire peut être considérée comme une source d'énergie quasi inépuisable et renouvelable, son exploitation nécessite de la convertir en combustibles stockables, tels que l'hydrogène (H 2 ). ([1], [START_REF] Lewis | Light work with water[END_REF]) Ce travail de doctorat constitue une étude amont dans le contexte général de la production d'hydrogène solaire par craquage photocatalytique de la molécule d'eau (photosynthèse artificielle ; illustration 1).

Illustration 1. Représentation schématique du processus du craquage de l'eau.

Deux réactions catalytiques combinées sont impliquées dans la photoproduction de l'hydrogène à partir de l'eau : la réaction d'oxydation de l'eau (WOR) et la réaction de dégagement d'hydrogène (HER). Ces réactions catalytiques intimement liées présentent des cinétiques différentes ce qui rend la mise en oeuvre du processus complet compliqué et peu efficace. Le développement de catalyseurs appropriés pour une meilleure efficacité est donc requis et suscite l'attention de la communauté scientifique mondiale.

Qu'ils s'agissent de catalyseurs moléculaires ou sous forme de nanomatériaux, la conception rationnelle des catalyseurs, ([3], [START_REF] Li | Nanoscale Advances in Catalysis and Energy Applications[END_REF]) ainsi que la compréhension de leurs propriétés photophysiques et catalytiques, sont de véritables défis à surmonter. Des nanoparticules métalliques (MNPs) se sont avérées des catalyseurs efficaces pour les réactions HE et WO, ([5]- [START_REF] Grigoriev | Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers[END_REF]) montrant des activités électrocatalytiques élevées, et une faible surtension. Contrairement aux métaux massifs, les nanoparticules sont dans un état de la matière finement divisé ce qui induit une surface spécifique élevée et une plus grande proportion de sites actifs. On peut en attendre une plus grande efficacité sous réserve de pouvoir en contrôler les caractéristiques.

Pour ce qui est de la HER, le platine demeure le métal de référence. Cependant, différents nanomatériaux à base de ruthénium présentant des compositions, morphologies, structures cristallines et tailles diverses ont été rapportés dans la littérature comme catalyseurs pour le processus du craquage de l'eau. Ainsi, des nanomatériaux de ruthénium ont été reportés comme des alternatives intéressantes aux catalyseurs à base de platine et de palladium pour la réaction de HE. [START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] L'amélioration des performances électrocatalytiques de nanoparticules de ruthénium (RuNPs) comparativement à une poudre de ruthénium massif a été établie et attribuée à la plus grande surface active que les RuNPs possèdent. Très récemment, le potentiel de RuNPs poreuses stabilisées par un mélange MeOH/THF et de RuNPs bien définies stabilisées par la 4phénylpyridine (illustration 2), pour la réaction de HE a été démontré. ([5], [START_REF] Drouet | A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions[END_REF])

Roberto González Gómez 355 L'originalité de ce travail tient dans l'utilisation d'un acide carboxylique comme stabilisant.

A notre connaissance, un seul exemple est rapporté dans la littérature, qui repose sur l'utilisation d'un C60 à fonctions acide carboxylique, C 66 (COOH) 12 ). [START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF] En parallèle, des calculs basés sur la théorie de la fonctionnelle de la densité (DFT) ont été effectués à partir d'un modèle de Ru 55 NP de structure de base hcp, (illustration 4) selon un modèle thermodynamique alimenté par des énergies de DFT. Une analyse systématique des propriétés des liaisons et de la structure électronique (densité des États, population de Crystal orbital Hamilton, charges atomiques) a été réalisée pour les différentes RuNPs stabilisées par les acides carboxyliques cités auparavant. La très bonne concordance des résultats obtenue entre les études de caractérisation théoriques et expérimentales a permis de conclure quant à l'efficacité des outils de chimie théoriques appliqués pour construire un modèle théorique fiable afin de décrire les RuNPs étudiées. Ce travail a donc montré que la chimie computationnelle peut être appliquée à la compréhension de petites nanoparticules, entre [1,0 à 2,0 nm], avec un niveau de précision et de pertinence similaire à celui connu en chimie moléculaire.

L'analyse du pMPA a mis en évidence une surface légèrement oxydée (ca. 0,35e) pour la composition de surface optimale De plus, pour cette composition, l'énergie d'adsorption de l'hydrogène calculée se situe dans la fourchette [-3,1 à -8,0 kcal.mol -1 ] pour les plans (001) et (101). Ce résultat est très intéressant car il montre l'intérêt potentiel de ces RuNPs en tant que catalyseur pour la réaction de HE dans l'électrolyse de l'eau (Illustration 8). [START_REF] Nørskov | Trends in the Exchange Current for Hydrogen Evolution[END_REF] Roberto González Gómez 361 Les synthèses réalisées en diminuant la quantité d'acide octanoïque (0,30 et 0,15 equiv. molaire) ont montré que même une faible quantité de ligand (0,15 equiv.) permet de stabiliser des RuNPs de petite taille et de forme régulière. Par IRFT, aucun signal attribuable à de l'acide octanoïque libre n'a été détecté mais la présence d'octanoate a été observée (illustration 13), ainsi que potentiellement du THF. Une étude a ensuite été menée en utilisant le pentane comme solvant de synthèse.

Roberto González Gómez 367 CO. SSB correspond à des bandes de rotation. Les modes de coordination du CO à la surface des NPs en relation avec les sites de surface libres sont indiqués. [START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] ΔG H* (kcal.mol Les résultats de ce chapitre, ont conduit à la conclusion qu'un catalyseur approprié pour la HER sera plutôt des RuNPs possédant un taux de couverture de leur surface moyen par un ligand ayant une longueur de chaîne alkyle moyenne.

En vue de synthétiser des systèmes hybrides RuNPs-PS, le chapitre suivant (n°4) est consacré à des réactions d'échange d'acides carboxyliques à la surface de RuNPs préformées.

Cette étude a été menée afin de trouver une alternative à la synthèse directe de RuNPs en présence du PS. En effet, les RuNPs étant connues pour être des catalyseurs actifs pour la réduction des arènes, [START_REF] Liu | Substrate-mediated enhanced activity of Ru nanoparticles in catalytic hydrogenation of benzene[END_REF]

  GENERAL INTRODUCTION ........................................................................................................................................... CHAPTER I GENERAL BACKGROUND ............................................................................................................................ 1.1 METAL NANOPARTICLES: INTERESTS, PROPERTIES AND APPLICATIONS ........................................................................................ 1.2 SYNTHESIS OF METAL NANOPARTICLES ...............................................................................................................................1.2.1 Synthesis of MNPs in Solution ........................................................................................................................... 1.2.2 Formation Mechanism of MNPs ....................................................................................................................... 1.2.3 Stabilization of MNPs ....................................................................................................................................... 1.2.4 Synthesis of MNPs by the Organometallic Approach ........................................................................................ 1.3 DFT FOR MODELING ORGANOMETALLIC NANOCATALYSTS ...................................................................................................... 1.3.1 Methods for Describing MNPs .......................................................................................................................... 1.3.2 Strategy Used to Define the Surface of MNPs ..................................................................................................1.4 RUTHENIUM NANOPARTICLES ........................................................................................................................................... 1.4.1 Synthesis of RuNPs ............................................................................................................................................ 1.4.2 Stabilization of RuNPs ....................................................................................................................................... 1.4.3 Experimental and Theoretical Characterization of RuNPs ................................................................................ 1.4.4 Modification of RuNPs by Ligand Exchange...................................................................................................... 1.5 INTEREST OF RUNPS IN CATALYSIS ..................................................................................................................................... CHAPTER II ETHANOIC ACID-CAPPED RUNPS: EXPERIMENTAL AND THEORETICAL STUDIES .........................................2.1 INTRODUCTION .............................................................................................................................................................. 2.2 SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF RUNPS ................................................................................................... 2.2.1 Organometallic Ruthenium Precursor .............................................................................................................. 2.2.2 Synthesis of Ethanoic Acid-Capped RuNPs ........................................................................................................ 2.2.2.1 Structural Characterization of RuNPs Stabilized with 0.2 equiv. of CH3COOH ................................................................ 2.2.2.2 Structural Characterization of RuNPs Stabilized with 0.4 equiv. of CH3COOH ................................................................ 2.3 STUDY OF THE ETHANOIC ACID INTERACTIONS WITH THE SURFACE OF RUNPS .............................................................................. 2.3.1 Proton-Liquid NMR Characterization ................................................................................................................ 2.3.2 Diffusion-Ordered Proton NMR Experiments .................................................................................................... 2.4 CARBOXYLIC ACID POSSIBLE DEPROTONATION ...................................................................................................................... 2.4.1 Carboxylic Adsorption Strengths and CH 3 COO-H Bond Dissociation ................................................................. 2.4.2 Solid-NMR Characterization ............................................................................................................................. 2.4.3 Vibrational Properties .....................................................................................................................................2.5 SURFACE COMPOSITION ................................................................................................................................................ 2.5.1 Experimental Titration of Surface Hydrides .................................................................................................... 2.5.2 DFT Titration of Surface Species ..................................................................................................................... 2.5.3 On the Possible Presence of THF at the NPs Surface ....................................................................................... 2.6 ELECTRONIC PROPERTIES ............................................................................................................................................... 2.6.1 Electronic States ............................................................................................................................................. 2.6.2 Atomic Charges in RuNP ................................................................................................................................. 2.7 HYDROGEN EVOLUTION REACTION: A POSSIBLE APPLICATION ................................................................................................ 2.8 CONCLUSION .............................................................................................................................................................. CHAPTER III CARBOXYLIC ACID-CAPPED RUNPS: USE OF LIGANDS WITH LONGER ALKYL CHAIN LENGTH ................... 3.A INTRODUCTION ........................................................................................................................................................... 3.1 PENTANOIC ACID-CAPPED RUNPS ................................................................................................................................... 3.1.1 Synthesis of RuNPs Stabilized by Pentanoic Acid ............................................................................................ 3.1.2 Adsorption Energies Analysis in Ru 55 NP Model Covered by Pentanoic Moieties............................................ Study of Ru x (C 4 H 9 COOH) 0.4 NPs ......................................................................................................... 3.1.4 DOSY 1 H-NMR Analysis of Ru x (C 4 H 9 COOH) 0.4 NPs ........................................................................................... 3.1.5 Infrared Interpretation of Ru x (C 4 H 9 COOH) 0.4 NPs ........................................................................................... 3.1.6 Ligand Coverage Optimization .......................................................................................................................

3. 1 . 6 . 1

 161 Synthesis of a Series of Rux(C4H9COOH)y NPs ................................................................................................................ 3.1.6.2 NMR Analysis of Rux(C4H9COOH)y NPs ...........................................................................................................................

3. 1 . 7

 17 Evaluation of Ru(C 4 H 9 COOH) 0.3 NPs ................................................................................................................

3. 1 . 7 . 1

 171 Solid-NMR Studies of Rux(C4H9COOH)0.3 NPs ................................................................................................................. 3.1.7.2 Elemental Analysis of Rux(C4H9COOH)0.3 NPs ................................................................................................................. 3.1.7.3 Theoretical Titration of Rux(C4H9COOH)0.3 NPs ..............................................................................................................

3. 1 . 8

 18 Theoretical Catalytic Assessing: HER Reaction ............................................................................................... 3.1.9 Conclusion ......................................................................................................................................................

FIGURE 2

 2 FIGURE 2.15 1 H-NMR (THF-D 8 ); (BLUE) RUX(CH3COOH)0.4 NPS; (RED) CH3COOH. ..............................................................................................................................

FIGURE 2 .

 2 FIGURE 2.16 [RU6] NANOCLUSTERS USED AS MODEL FOR THE DFT CHEMICAL SHIFT CALCULATIONS. ................................................................................................................

FIGURE 2 .

 2 FIGURE 2.17 DFT MEAN METHYL PROTONS CHEMICAL SHIFT OF (A) ETHANOIC ACID DIMER & (B) ETHANOATE. ...................................................................................................

FIGURE 2 .

 2 FIGURE 2.18 DFT MEAN METHYL PROTONS CHEMICAL SHIFT OF CH3COOH INTERACTING WITH [RU6] NANOCLUSTER IN DIFFERENT COORDINATION MODES; (A) Η; (B) Μ. ......................

FIGURE 2 . 3 ;(

 23 FIGURE 2.19 DFT MEAN METHYL PROTONS CHEMICAL SHIFT OF CH3COO MOIETY INTERACTING WITH [RU6] NANOCLUSTER IN DIFFERENT COORDINATION MODES; (A) CHAIR: Σ CARBON, Μ 3 ;

FIGURE 2 .

 2 FIGURE 2.20 DFT MEAN METHYL PROTONS CHEMICAL SHIFT OF TWO CH3COO MOIETIES INTERACTING WITH MG 2+ . ..........................................................................................

FIGURE 2 8 )

 28 FIGURE 2.21 EXPERIMENTAL 1 H-NMR (THF-D 8 ) OF RUX(CH3COOH)0.4 NPS (BLUE) IN COMPARISON WITH FREE CH3COOH (RED). DFT 1 H-NMR CHEMICAL SHIFTS OF THE METHYL GROUP IN VARIOUS MODELS ((CH3COOH)2, CH3COO -, [RU6] CLUSTERS). ...................................................................................................................................

FIGURE 2 8 )

 28 FIGURE 2.22 DIFFUSION-FILTERED DOSY 1 H-NMR (THF-D 8 ) SPECTRUM OF RUX(CH3COOH)0.4 NPS. ..........................................................................................................

Η

  , (C) CH3COOH; Σ CARBON, Μ, (D) CH3COO; Σ CARBON, Μ 3 & (B) FREE CH3COO......................................................................................................................

FIGURE 2 .

 2 FIGURE 2.30 CARBOXYLIC CARBON DFT CHEMICAL SHIFT OF THE CARBOXYLIC MOIETIES INTERACTING WITH [RU6] NANOCLUSTER. DIFFERENT COORDINATION MODES (A) CH3COOH; Η & (B) CH3COO; Μ. ..................................................................................................................................................................................................................

FIGURE 2 .

 2 FIGURE 2.31 EXPERIMENTAL 13 C SOLID-NMR OF RUX(CH3COOH)0.4 NPS AND DFT 13 C-NMR CHEMICAL SHIFTS OF THE METHYL (RED) AND CARBOXYLIC CARBON (BLUE) IN VARIOUS MODELS ((CH3COOH)2, CH3COO -& [RU6] CLUSTERS). ........................................................................................................................................................

FIGURE 2 .

 2 FIGURE 2.32 EXPERIMENTAL FTIR SPECTRUM OF RUX(CH3COOH)0.4 NPS AND MAIN PEAKS ASSIGNMENTS. THE EXPERIMENTAL PEAKS POSITION AND ASSIGNMENT OF SODIUM ETHANOATE (CH3COONA) ARE ALSO INDICATED: IN THE SOLID (GREEN) AND LIQUID STATE (PURPLE). Ν: STRETCHING; Δ: BENDING; Ρ: ROCKING; Ω: WAGGING; SS OR S: SYMMETRIC; AS: ASYMMETRIC. ................................................................................................................................................................................................................

.FIGURE 3 .

 3 FIGURE 3.16 1 H-NMR (THF-D 8 ) OF RUNPS; (RED PROFILE) RUX(C4H9COOH)0.20; (BLUE PROFILE) RUX(C4H9COOH)0.30. PEAKS ATTRIBUTED TO SIDE PRODUCTS ARE DENOTED WITH AND "X" AND THE PEAKS FOR PENTANOIC ACID ARE GIVEN AS BARS AT THE BOTTOM OF THE FIGURE...........................................................................................................

FIGURE 3 . 17

 317 FIGURE 3.17

13 CFIGURE 3 .FIGURE 3 . 1 )FIGURE 3 .FIGURE 3 .

 1333133 FIGURE 3.18 SOME OF THE SELECTED RU55 NP OPTIMIZED STRUCTURES WITH DIFFERENT LIGAND SURFACE COVERAGE (C4H9COO & H)................................................................FIGURE 3.19 ΔAG° (𝒑𝑯𝟐, [C4H9COOH]) PHASE DIAGRAM FOR H2 (GAS) AND C4H9COOH (LIQUID) ADSORPTION ON RU55 NP AT 300 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L -1).

FIGURE 3 .

 3 FIGURE 3.26 1 H-NMR (THF-D 8 ) OF (RUX(C7H15COOH)0.4)THF (RED PROFILE) VS FREE C7H15COOH (BLUE PROFILE). SIDE PRODUCTS ARE DENOTED AS "X" AND THE PROTON ASSIGNATION IS DISPLAYED AT THE BOTTOM. ...........................................................................................................................................................................................

FIGURE 3 .

 3 FIGURE 3.27 RU55 NP OPTIMIZED MODELS WITH DIFFERENT COVERAGE VALUES OF CARBOXYLIC ACID ENTITIES. ................................................................................................

FIGURE 3 .

 3 FIGURE 3.28 TEM MICROGRAPH OF (A) (RUX(C7H15COOH)0.15)THF NPS; SCALE BAR: 100 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL -A-RUNPS. TEM MICROGRAPH OF (C) (RUX(C7H15COOH)0.30)THF NPS; SCALE BAR: 50 NM; (D) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL -C-RUNPS. .......................................................................FIGURE 3.29 EXPERIMENTAL FTIR SPECTRA: (A) (RUX(C7H15COOH)0.15)THF; (B) (RUX(C7H15COOH)0.30)THF;(C) (RUX(C7H15COOH)0.40)THF NPS. THREE SPECIFIC VIBRATION REGIONS ARE HIGHLIGHTED: (BLUE) Ν(CO); (GREEN) Ν(COOH); (ORANGE) Ν(COO). .....................................................................................................................................

1 HFIGURE 3 .FIGURE 3 .FIGURE 3 .

 1333 FIGURE. ........................................................................................................................................................................................................................FIGURE 3.45 TEM MICROGRAPHS OF RUX(C7H15COOH)0.20 +0.20 NPS; (A) GENERAL VIEW, SCALE BAR: 200 NM; (B) FOCUS ON THE NANOSYSTEMS, SCALE BAR: 50 NM; (C) MICROGRAPH OF INITIAL RUX(C7H15COOH)0.20 NPS; SCALE BAR: 50 NM. ......................................................................................................................................................... FIGURE 3.46 NOESY-NMR SPECTRUM (C6D6) OBTAINED FOR RUX(C7H15COOH)0.20 +0.20 NPS. POSITIVE NOE IS HIGHLIGHTED IN GREEN CIRCLES. ...............................................FIGURE 3.47 COORDINATION MODES OF CO AT THE NPS SURFACE IN RELATION WITH THE FREE SURFACE SITES. [93] ...........................................................................................

FIGURE 5 . 5 1 )FIGURE 6 .2 1 H

 55161 FIGURE 5.5 OPTIMIZED THEORETICAL MODELS FOR THE INTERACTION OF PS3 (LEFT) & PS4 (RIGHT) MOLECULES WITH RU55(CH3COO)2(H)2 NP. THE EADS (KCAL.MOL -1 ) ARE ALSO PRESENTED. ...................................................................................................................................................................................................................FIGURE 5.6 OPTIMIZED THEORETICAL MODELS FOR THE INTERACTION OF (A) PS1, (B) PS2 AND (C) PS4 MOLECULES WITH RU55(CH3COO)10(H)27 NP AND CORRESPONDING EADS (KCAL.MOL -

  THE DATA CORRESPOND TO THE ADDITION OF 0.10 EQUIV. OF EACH INCOMING LIGAND. ............................................................................................................................... TABLE 5.1 COMPARISON OF ADSORPTION ENERGIES FOR DIFFERENT PS ONTO RU55 NP WITH LOW AND INTERMEDIATE SURFACE COVERAGE WITH THAT OF TWO ETHANOATES IN THE SAME CONDITIONS. ................................................................................................................................................................................................................. TABLE 5.2 DFT REACTION ENERGIES FOR THE LIGAND EXCHANGE REACTION BETWEEN RU55(CH3COO)12(H)29 NP AND PS1 & PS4..................................................................... TABLE 5.3 COMPARISON OF ADSORPTION ENERGIES FOR PS1 ONTO DIFFERENT RU55 NP MODELS (AT LOW, INTERMEDIATE AND HIGH SURFACE COVERAGE RATIO) WITH THAT OF TWO ETHANOATES IN THE SAME CONDITIONS. ............................................................................................................................................................................... TABLE 5.4 DFT REACTION ENERGY FOR THE LIGAND EXCHANGE REACTION BETWEEN RU55(CH3COO)16(H)33 NP AND PS1 ................................................................................ TABLE 6.1. DIFFERENT QUANTITIES OF LIGAND USED FOR RUNPS SYNTHESIS. ............................................................................................................................................ TABLE 6.2 BENZENE AND THF VISCOSITY IN RELATION WITH THEIR TEMPERATURE. .....................................................................................................................................

  4 HYDROGEN COVERAGE RATIO, RU55 NP ADSORPTION SITE OF ETHANOIC ACID AND COORDINATION MODE, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND ETHANOIC ACID ADSORPTION ENERGY. ......................................................................................................................................................................................................TABLE A.5 HYDROGEN AND THF COVERAGE RATIO, THF ADSORPTION SITE IN Η MODE, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND THF MEAN ADSORPTION ENERGY. .................. TABLE A.6 ETHANOATE & HYDROGEN COVERAGE RATIOS, (CH3COO) & H COORDINATION MODES, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND CARBOXYLIC MOIETY MEAN ADSORPTION ENERGY. ....................................................................................................................................................................................................................... TABLE B.1 PENTANOATE & HYDROGEN COVERAGE RATIOS, (C4H9COO) & H COORDINATION MODES, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND PENTANOATE MEAN ADSORPTIONENERGY. ....................................................................................................................................................................................................................... TABLE B.2 OCTANOATE & HYDROGEN COVERAGE RATIOS, (C7H15COO) & H COORDINATION MODES, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND OCTANOATE MEAN ADSORPTION ENERGY. ....................................................................................................................................................................................................................... TABLE B.3 STUDIED CARBOXYLIC MOIETIES DEPOSED ONTO THE SAME ADSORPTION SITE OVER THE PLANE [100], DFT ENERGY OF THE OPTIMIZED STRUCTURE AND CARBOXYLIC MOIETY ADSORPTION ENERGY. ......................................................................................................................................................................................................TABLE B.4 OCTANOATE, BENZOATE & H COVERAGE RATIOS, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND CARBOXYLIC MEAN ADSORPTION ENERGY. ........................................... TABLE B.5 DFT ENERGY OF THE OPTIMIZED RU55(CH3COO)2(H)2 STRUCTURES INTERACTING WITH DIFFERENT PHOTOSENSITIZER AND ITS ADSORPTION ENERGY. ................................. TABLE B.6 DFT ENERGY OF THE OPTIMIZED RU55(CH3COO)10(H)27 STRUCTURES INTERACTING WITH DIFFERENT PHOTOSENSITIZER AND ITS ADSORPTION ENERGY. .............................. TABLE B.7 DFT ENERGY OF THE OPTIMIZED RU55(CH3COO)14(H)31 STRUCTURES INTERACTING WITH PS1 AND ITS ADSORPTION ENERGY. .............................................................. TABLE C.1 ETHANOATE & HYDROGEN COVERAGE RATIOS, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND ETHANOIC ACID ADSORPTION ENERGY. ................................................... TABLE C.2 ETHANOATE & HYDROGEN COVERAGE RATIOS, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND THF MEAN ADSORPTION ENERGY. ........................................................ TABLE C.3 ETHANOATE & HYDROGEN COVERAGE RATIOS, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND THF MEAN ADSORPTION ENERGY. ........................................................ TABLE D.1 HYDROGEN COORDINATION MODES AND THEIR CORRESPONDING VIBRATIONAL FREQUENCIES (RU-H) ONTO RU55 NP. ......................................................................... TABLE D.2 ETHANOIC ACID COORDINATION MODE AND ITS CORRESPONDING VIBRATIONAL FREQUENCIES(RU-COOH) ONTO RU55 NP. ................................................................. TABLE D.3 ETHANOATE COORDINATION MODES AND THEIR CORRESPONDING VIBRATIONAL FREQUENCIES (RU-COO) ONTO RU55 NP. ...................................................................

ABBREVIATIONS 20 

 20 ABBREVIATIONS

Figure 1 . 2

 12 Figure 1.2 Representation of the quantum size effect and discrete electronic energy levels in MNPs.

Scheme 1 . 1

 11 Scheme 1.1 Mechanism of formation of MNPs described for the metal salt reduction method.

Figure 1 . 7

 17 Figure 1.7 Representation of stabilized MNP.

Figure 1 .

 1 Figure 1.11 Ru 55 hcp cluster in a unit cell optimized by VASP..

  cyclooctadiene)(1,3,5-cyclooctriene) ([Ru(COD)(COT)]) which represents an ideal compound due to its fast decomposition at low temperature (≤ r.t.) and low gas pressure ([1 -3 bar] H 2 ). Another important advantage is that the hydrogenation of this precursor releases only cyclooctane as side product, which is inert towards the metal surface and can be easily removed under high-vacuum.

Figure 1 .

 1 Figure 1.12 Representation of organometallic precursor used to synthetize RuNPs. [Ru 3 (CO) 12 ], [Ru(COD)(η 3 -C 3 H 5 ) 2 ], [Ru(COD)(COT)], respectively.

Figure 1 .

 1 Figure 1.16 Representation of the selective hydrogenation catalysis performed on RuNPs.

Figure 2 . 1

 21 Figure 2.1 Nanomaterials size in comparison with organic and inorganic structures.

Figure 2 . 3

 23 Figure 2.3 Metal nanoparticle protected by: (a) polymer; (b) ligand molecules.[150]

Figure 2 . 4 .

 24 Figure 2.4. (a) Different type of ligands used for stabilizing RuNPs;[START_REF] Martínez-Prieto | Organometallic Ruthenium Nanoparticles: Synthesis, Surface Chemistry, and Insights into Ligand Coordination[END_REF] (b) reaction pathways for the formic acid decomposition.[START_REF] Grasemann | Environmental Science Formic acid as a hydrogen source -recent developments and future trends[END_REF]

Figure 2 . 5

 25 Figure 2.5 Synthesis of Ru x (C 66 (COOH) 12) y nanoparticles.[START_REF] Serp | Hexakis [ 60 ] Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties[END_REF]

Figure 2 . 6

 26 Figure 2.6 Gold model nanoparticle covered by p-mercaptobenzoic acid (Au 102 (p-MBA) 44) and their different coordination modes.[START_REF] Häkkinen | Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts[END_REF]

Scheme 2 . 3

 23 Scheme 2.3 Synthesis of RuNPs stabilized by 0.2 equiv. of ethanoic acid.

Figure 2 . 7

 27 Figure 2.7 TEM micrographs of Ru x (CH 3 COOH) 0.2 NPs sample; (a) ruthenium superstructures; scale bar: 1000 nm; (b) ultra-small RuNPs; scale bar: 50 nm; (c) size histogram of individual RuNPs.

Figure 2 . 8

 28 Figure 2.8 HRTEM of Rux(CH 3 COOH) 0.2 individual NPs.

Figure 2 .

 2 Figure 2.9 (a) Dark field micrograph of Ru x (CH 3 COOH) 0.2 NPs with two different highlighted spots; EDX spectra analysis of (b) 001 spot corresponding to a zone with RuNPs and (c) 002 spot for the metal free carbon-covered grid.

  Characterization of RuNPs Stabilized with 0.4 equiv. of CH 3 COOH Following the observations obtained in the previous experiments, a synthesis of RuNPs was repeated in the same conditions as for Ru x (CH 3 COOH) 0.2 NPs. But with the particularity of increasing 100.0 % the quantity of stabilizing agent, the ratio [CH 3 COOH]/[Ru] was raised to 0.4 equiv. (Ru x (CH 3 COOH) 0.4 ; (scheme 2.4)).

Scheme 2 . 4

 24 Scheme 2.4 Synthesis of RuNPs stabilized by 0.4 equiv. of ethanoic acid.

Figure 2 .

 2 Figure 2.10 (a) TEM micrograph of Ru x (CH 3 COOH) 0.4 NPs, scale bar: 50nm; (b) corresponding size histogram of RuNPs.

  crystalline structure. Fast Fourier Transformation (FFT) on the red highlighted spot of HRTEM micrograph, indicated the presence of interplanar distances of 0.238 and 0.208 nm that can be attributed to crystalline (100) and (101) plans of the bulk ruthenium hexagonal close packed (hcp) structure (figure 2.11 b). Moreover, the isolated particle presents a Miller pattern of [1 ̅ 21 ̅ 3] (figure 2.11 c). In general, NPs showed a similar low crystallinity degree, which is another indicative that corroborate the formation of a homogenous system.

Figure 2 .

 2 Figure 2.11 HRTEM analysis of Ru x (CH 3 COOH) 0.4 NPs; (a) micrograph; (b) FFT (c) Miller pattern.

Figure 2 .

 2 Figure 2.12 (a) WAXS spectrum of Ru x (CH 3 COOH) 0.4 NPs; (b) RDFs comparison in real space; Ru x (CH 3 COOH) 0.4 (red) vs Ru hcp crystalline structure computed for 30 Ru atoms (green).

Figure 2 .

 2 Figure 2.13 WAXS spectra recorded from Ru x (CH 3 COOH) 0.4 NPs; (red) freshly prepared sample; t = 0; (green) stored for long time; t = 1 year.

Figure 2 .

 2 Figure 2.14 (a) Dark field micrograph of Ru x (CH 3 COOH) 0.4 NPs with two analyzed highlighted spots; EDX spectra analyses of (b) 004 and (c) 005 spot corresponding to free carbon-covered grid zone and to deposited RuNPs, respectively.

  ) and acid proton (RCOOH) of the ethanoic acid, respectively, according to the signals provided by the spectrum recorded for the free ligand.

Figure 2

 2 Figure 2.151 H-NMR (THF-d 8 ); (blue) Ru x (CH 3 COOH) 0.4 NPs; (red) CH 3 COOH.

Figure 2 . 16 [

 216 Figure 2.16 [Ru 6 ] nanoclusters used as model for the DFT chemical shift calculations.

Figure 2 .

 2 Figure 2.17 DFT mean methyl protons chemical shift of (a) ethanoic acid dimer & (b) ethanoate.

(

  Mg 2+ ) showed a deshielding of ca. 0.8 ppm, resulting in a chemical shift of 2.1 ppm (figure 2.20).

Figure 2 .

 2 Figure 2.20 DFT mean methyl protons chemical shift of two CH 3 COO moieties interacting with Mg 2+ .

Figure 2 8 )

 28 Figure 2.21 Experimental 1 H-NMR (THF-d 8 ) of Ru x (CH 3 COOH) 0.4 NPs (blue) in comparison with free CH 3 COOH (red). DFT

Figure 2 8 )

 28 Figure 2.22 Diffusion-filtered DOSY 1 H-NMR (THF-d 8 ) spectrum of Ru x (CH 3 COOH) 0.4 NPs.

1 Figure 2 .

 12 Figure 2.23 Diffusional attenuation of the [1.9 -2.2 ppm] area for Ru x (CH 3 COOH) 0.4 NPs dispersed in THF-d 8 at r.t. Data were analyzed with a bi-exponential least-square fitting.

Scheme 2 .

 2 Scheme 2.5 (a) Hydrodynamic diameter representation and (b) fast exchanging ligand proposed.

Figure 2 .

 2 Figure 2.24 Theoretical models used for studying the ethanoic acid interaction with (a) Ru 55 NP; model 1 & (b) Ru 55 (CH 3 COO) 15 H 32 NP; model 2. The faceting of the surface is highlighted with translucent gray planes.

Figure 2 .

 2 Figure 2.25 Energy profile of the CH 3 COO-H bond dissociation. Black profile: O-H activation on the Ru 55 NP (model 1); red profile: O-H activation on the Ru 55 (CH 3 COO) 15 H 32 NP (model 2). Geometries are shown for the model 1, similar parameters were found in model 2. Energies are given in kcal.mol -1 . Some characteristic bond lengths are also given, in Å (same color convention as the energy profiles).

  found at 126.3 & 142.8 ppm. As it will be observed, these two signals cannot be completely ignored because they could represent a chair coordination mode of the ethanoate onto the RuNPs.

Figure 2 .26 13 C

 213 Figure 2.26 13 C CP Hahn-MAS NMR of Ru x (CH 3 COOH) 0.4 NPs diluted in porous silica.

Figure 2 .

 2 Figure 2.27 DFT mean chemical shift of the carboxylic carbon atoms in the ethanoic acid dimer.

Figure 2 .

 2 Figure 2.28 Methyl carbon DFT chemical shift of the ethanoic moieties interacting with [Ru 6 ] nanocluster. Different coordination modes (a) CH 3 COOH; σ carbon, μ, (b) CH 3 COO; μ, (c) CH 3 COO; η & (d) CH 3 COOH; η.

Figure 2 .

 2 Figure 2.29 Carboxylic carbon DFT chemical shift of the carboxylic moieties free and interacting with [Ru 6 ] nanocluster. Different coordination modes (a) CH 3 COO; η, (c) CH 3 COOH; σ carbon, μ, (d) CH 3 COO; σ carbon, μ 3 & (b) free CH 3 COO.

Figure 2 .

 2 Figure 2.30 Carboxylic carbon DFT chemical shift of the carboxylic moieties interacting with [Ru 6 ] nanocluster. Different coordination modes (a) CH 3 COOH; η & (b) CH 3 COO; μ.

Figure 2 .31 Experimental 13 C

 213 Figure 2.31 Experimental 13 C solid-NMR of Ru x (CH 3 COOH) 0.4 NPs and DFT 13 C-NMR chemical shifts of the methyl (red) and carboxylic carbon (blue) in various models ((CH 3 COOH) 2 , CH 3 COO -& [Ru 6 ] clusters).

Figure 2 .

 2 Figure 2.32 Experimental FTIR spectrum of Ru x (CH 3 COOH) 0.4 NPs and main peaks assignments. The experimental peaks position and assignment of sodium ethanoate (CH 3 COONa) are also indicated: in the solid (green) and liquid state (purple). ν: stretching; δ: bending; ρ: rocking; ω: wagging; ss or s: symmetric; as: asymmetric.

Figure 2 .

 2 Figure 2.33 Experimental FTIR spectrum of Ru x (CH 3 COOH) 0.4 NPs and theoretical harmonic frequencies calculated for model 2 CH 3 COO*, H* (blue: Ru-H modes; red: Ru-ethanote modes). The signals of CH 3 COONa are also shown.

Gómez 105 Thus

 105 Scheme 2.7 Surface hydrides titration by a catalytic reduction of 2-norbornene in the presence of Ru x (CH 3 COOH) 0.4 NPs.

Figure 2 .

 2 Figure 2.35 Δ a G° (𝑝 𝐻 2 , [CH 3 COOH]) phase diagram for H 2 (gas) and CH 3 COOH (liquid) adsorption on Ru 55 NP at 300 K (pressure in bar, concentration in mol.L -1

Figure 2 .

 2 Figure 2.37 Δ a G° (𝒑 𝑯 𝟐 , [CH 3 COOH]) phase diagram for H 2 (gas) and CH 3 COOH (liquid) adsorption on Ru 55 NP at 200 K (pressure in bar, concentration in mol.L -1

Figure 2 .

 2 Figure 2.39 Δ a G° (𝒑 𝑯 𝟐 , [CH 3 COOH]) phase diagram for H 2 (gas) and CH 3 COOH (liquid) adsorption on Ru 55 NP at 450 K (pressure in bar, concentration in mol.L -1

Figure 2 .

 2 Figure 2.41 TEM micrographs of Ru x (THF) y NPs; (a) Ru agglomerates; scale bar: 200 nm; (b) RuNPs; scale bar: 50 nm; (c) size histogram of individual RuNPs.

Figure 2 .

 2 Figure 2.42 Optimized geometry of Ru 55 (CH 3 COO) 15 (H) 32 (THF).

Figure 2 .

 2 Figure 2.43 Δ a G° (𝒑 𝑯 𝟐 , [THF]) phase diagram for H 2 (gas) and THF (liquid) adsorption on Ru 55 NP at 300 K (pressure in bar, concentration in mol.L -1

compositions (domains 46

 46 , 49 & 52) are found when 𝑝 𝐻 2 and [THF] are in the range [10 -5 -10 -2 bar]. These structures possess the same amount of hydrogen but different quantity of THF according to its concentration under equilibrium (figure 2.44), their coordinates are given in section appendix F.

Figure 2 .

 2 Figure 2.44 More stable [Ru 55 ] clusters found at 300 K. (Domain 46: Ru 55 (THF)(H) 53 ; domain 49: Ru 55 (THF) 2 (H) 53 ; domain 52: Ru 55 (THF) 3 (H) 53 ).

  properties of the model 2 CH 3 COO*, H* were compared with those of the bare Ru 55 NP covered with hydrides, and even capped by carbon monoxide. The d-band center for the 44 surface ruthenium atoms in the model 2 CH 3 COO*, H* was found to be at 2.94 eV below the Fermi energy (𝜀̅ 𝑑 ), meanwhile the 11 core atoms have a 𝜀̅ 𝑑 = 3.34 eV. In comparison with the bare Ru 55 , which displays a d-band center that lies at 2.60 eV & 3.60 eV for surface and core atoms, respectively as shown on the projected density of states (pDOS) plotted (figure 2.45). It appears that the addition of 16 ethanoates and 33 hydrides stabilizes the nanoparticle surface atoms in ca. 7.8 kcal.mol -1 .

Figure 2 .

 2 Figure 2.45 Projected COHP & DOS profiles for Ru x (CH 3 COO) 16 (H) 33 NP model. Dashed red line and dotted red line on the pDOS profile: d-band center of surface and core Ru atoms, respectively; brown line: Fermi energy. The backdonation observed is also highlighted.

  bond strength, with the IpCOHP index per Ru-Ru bond equals to 19.6 kcal.mol -1 for 2 CH 3 COO*, H* instead of 27.0 kcal.mol -1 in the bare Ru 55 NP. In other words, the coordination of surface ethanoate involves a lowering by ca. 30% the cohesive energy of the metal part of the Ru 55 NP.

  Three different models were considered to analyze the progress of the oxidation as a function of the ligand surface coverage. Thus, the pMPA charges were calculated for the bare Ru 55 NP, the moderately hydrogenated Ru 55 NP (Ru 55 (H) 17 ) and the 2 CH3COO*, H* model (Ru 55 (CH 3 COO) 16 (H) 33 ). The results are graphically compared in figure 2.46.

Figure 2 .

 2 Figure 2.46 Atomic pMPA charges shown as color maps. (a) Ru 55 ; (b) Ru 55 (H) 17 ; (c) Ru 55 (CH 3 COO) 16 (H) 33 . The charge scale is shown on the left. Charges are also shown: global (𝑞 𝑅𝑢 ), core (𝑞 𝑅𝑢 𝑐 ), surface ruthenium atoms (𝑞 𝑅𝑢 𝑠 ) and ligand (𝑞 𝐻𝑦𝑑𝑟𝑖𝑑𝑒 , 𝑞 𝐶𝑂𝑂 & 𝑞 𝑀𝑒 ).

  2.11) on five representatives surfaces sites of the bare Ru 55 NP, and compared with those of the stable CH 3 COO/H covered NP models; Ru 55 (CH 3 COO) 16 (H) 16 (domain 39) and of Ru 55 (CH 3 COO)(H) 54 (domain 7), which involve interactions with the planes (001) and (101) and the surrounding area of B 4 & B 5 surface sites of the Ru 55 NP model (see section 6.2.1). The ΔG H* values (see section appendix E.1) are presented in the figure 2.47, together with the atomic d-band center shown as color map.[START_REF] Del Rosal | Ligand-Field Theory-Based Analysis of the Adsorption Properties of Ruthenium Nanoparticles[END_REF]

Figure 2 . 1 )

 21 Figure 2.47 atom d-band center is shown as color map (scale in eV) for (a) Ru 55 (CH 3 COO) 16 (H) 16 , (b) Ru 55 (CH 3 COO)(H) 54 and (c) Ru 55 . The ΔG H* are given (kcal.mol -1 ) and the arrows indicate the adsorption sites. The surface, core and total average d-band center values are also presented (eV).

Figure 3 . 2

 32 Figure 3.2 Ru 55 NP model stabilized by (a) pentanoic acid and (b) octanoic acid.

  Scheme 3.2 Synthesis of RuNPs stabilized by 0.4 equiv. of pentanoic acid (Ru x (C 4 H 9 COOH) 0.4 ). The resulting nanoparticle is coverage for pentanoate and hydrides as it is expected from chapter II.

  3.1). At low magnification (figure 3.3 a), a self-organization of the particles was observed which is attributed to a solvent evaporation effect during the preparation of the grid CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 144 (coffee ring phenomenon). TEM micrographs recorded at higher magnification (figure 3.3 b) evidenced the presence of ultra-small nanoparticles which are difficult to distinguish, but its presence was corroborated by calculating the hydrodynamic radii obtained by DOSY NMR studies (vide infra). The size distribution built by measuring ca. 400 nanoparticles led to a mean size of ca. 1.13 ± 0.31 nm (figure 3.3 c).

Figure 3 . 3

 33 Figure 3.3 TEM micrographs of Ru x (C 4 H 9 COOH) 0.4 NPs; (a) self-organized NPs due to solvent evaporation; scale bar: 500 nm; (b) ultra-small RuNPs; scale bar: 50 nm; (c) size histogram of individual RuNPs.

  obtained about the stabilizing mechanism of ethanoic acid in the RuNPs, in particular the easy O-H activation. Twelve ethanoates were settled on the Ru 55 NP model in the presence of the same amount of hydrides coming from the carboxylic acid deprotonation (figure 3.4; model I). A similar model was built but this time with twelve pentanoates and the same quantity of hydrides (figure 3.4; model II). After structural optimization

Figure 3 . 4

 34 Figure 3.4 Ru 55 NP models with a high coverage value of carboxylate and hydrides entities; model 1: Ru 55 (CH 3 COO) 12 (H) 12 ; model II Ru 55 (C 4 H 9 COO) 12 (H) 12 .

  1 H-NMR (THF-d 8 ):  0.90 (t, 3H), 1.35 (sextet, 2H), 1.55 (quintet, 2H), 2.21 (t, 2H), 10.29 (s, 1H) ppm (figure 3.5 red profile). When comparing with the spectrum of the free pentanoic acid, the 1 H-NMR spectrum of Ru x (C 4 H 9 COOH) 0.4 NPs (figure 3.5 blue profile) shows an important broadening between [2.5 & 0.5 ppm]. This phenomenon is well-known to be indicative of a direct interaction between capping ligands and the RuNPs surface (see section 2.3.1) and derives from a decreased mobility. Also, apart from signals attributed to THF and grease, only two signals are well-distinguished at ca. 0.92 & 1.

Figure 3

 3 Figure 3.51 H-NMR (THF-d 8 ); (blue) Ru x (C 4 H 9 COOH) 0.4 NPs; (red) C 4 H 9 COOH.

Scheme 3 . 3

 33 Scheme 3.3 Proposed configuration for Ru x (C 4 H 9 COOH) 0.4 NPs according to solution 1 H-NMR spectroscopy.

Figure 3 8 )

 38 Figure 3.6 Diffusion-filtered DOSY 1 H-NMR (THF-d 8 ) spectrum of Ru x (C 4 H 9 COOH) 0.4 NPs.

Figure 3 . 7

 37 Figure 3.7 Experimental FTIR spectrum of Ru x (C 4 H 9 COOH) 0.4 NPs and main peaks assignments. Experimental characteristic peaks of pentanoic acid (green bars, C 4 H 9 COOH) and THF (yellow bars) are also indicated. ν: stretching; δ: bending; s: symmetric; as: asymmetric. Peaks attributed for coordinated THF at the RuNPs surface are likewise shown (blue).

  Ru x (C 4 H 9 COOH) 0.4 NPs compared to Ru x (CH 3 COOH) 0.4 NPs. In addition, with Ru x (C 4 H 9 COOH) 0.4 NPs a THF degradation is also observed.

1 . 1 ,

 11 just changing the [ligand]/[metal] ratio from [0.05 to 0.60 equiv.]. In each case, the yellow solution obtained after mixing in pentane the [Ru(COD)(COT)] precursor and pentanoic acid ligand, turned blackish after ca. 4 min of pressurizing the Fisher-Porter reactor with 3 bar of hydrogen under inert atmosphere. This change of color is a well-known indicative for the formation of RuNPs.

Figure 3 . 8

 38 Figure 3.8 TEM micrographs of Ru x (C 4 H 9 COOH) 0.05 NPs; (a) & (b) agglomeration of particles; scale bar: 50 nm & 500 nm, respectively.

Figure 3 .

 3 Figure 3.9 (a) TEM micrograph of Ru x (C 4 H 9 COOH) 0.05 NPs; scale bar: 50 nm; (b) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3.10 (a) TEM micrograph of Ru x (C 4 H 9 COOH) 0.20 NPs; scale bar: 50 nm; (b) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3.11 (a) TEM micrograph of Ru x (C 4 H 9 COOH) 0.30 NPs; scale bar: 50 nm; (b) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3.12 (a) TEM micrograph of Ru x (C 4 H 9 COOH) 0.50 NPs; scale bar: 50 nm; (b) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3. 13 TEM micrograph of Ru x (C 4 H 9 COOH) 0.60 NPs; scale bar: 50 nm; (b) corresponding size histogram of individual RuNPs.

Figure 3 8 )

 38 Figure 3.141 H-NMR (THF-d 8 ) of RuNPs; (1) Ru x (C 4 H 9 COOH) 0.05 ; (2) Ru x (C 4 H 9 COOH) 0.20 ; (3) Ru x (C 4 H 9 COOH) 0.30 ; (4) Ru x (C 4 H 9 COOH) 0.40 ; (5) Ru x (C 4 H 9 COOH) 0.50 ; (6) Ru x (C 4 H 9 COOH) 0.60 . Peaks attributed to side products are denoted with an "x" and the signals for pentanoic acid peaks are displayed in bars at the bottom of the figure. The signal surrounded by an orange circle corresponds to free ligand.

Figure 3 .

 3 Figure 3.15 provides a comparison of the 1 H NMR spectra (zoom of [0.6 -2.4 ppm] region)

Figure 3 8 )

 38 Figure 3.151 H-NMR (THF-d 8 ) of RuNPs; (group 1, brown profile), Ru x (C 4 H 9 COOH) 0.05 ; (group 2, green profile), Ru x (C 4 H 9 COOH) 0.30 ; (group 3, purple profile), Ru x (C 4 H 9 COOH) 0.60 . Peaks attributed to side products are denoted with an "x" and those of pentanoic acid are displayed in bars at the bottom of the figure.

  stabilized by 0.20 equiv. of pentanoic acid vs that of 0.30 equiv. (figure3.16, red and blue respectively).The same observation can be done as for previous comparison: a broadness increase of the signals is observed with higher quantity of ligand. Meaning that more ligands are interacting with RuNPs surface from 0.30 vs. 0.20 equiv. of pentanoic acid added. But differently from previous comparison, this leads to a more homogeneous population of NPs and not to smaller ones (similar size of ca. 1.5 nm for both RuNPs systems).

Figure 3 8 )

 38 Figure 3.161 H-NMR (THF-d 8 ) of RuNPs; (red profile) Ru x (C 4 H 9 COOH) 0.20 ; (blue profile) Ru x (C 4 H 9 COOH) 0.30 . Peaks attributed to side products are denoted with and "x" and the peaks for pentanoic acid are given as bars at the bottom of the figure.

Figure 3 . 17

 317 Figure 3.17

13 C

 13 CP Hahn-MAS NMR of Ru x (C 4 H 9 COOH) 0.3 NPs diluted in porous silica. Pentanoic acid peaks are given in bars at the bottom of the figure.

Figure 3 .

 3 Figure 3.18 Some of the selected Ru 55 NP optimized structures with different ligand surface coverage (C 4 H 9 COO & H).

Figure 3 .

 3 Figure 3.19 Δ a G° (𝒑 𝑯 𝟐 , [C 4 H 9 COOH]) phase diagram for H 2 (gas) and C 4 H 9 COOH (liquid) adsorption on Ru 55 NP at 300 K (pressure in bar, concentration in mol.L -1

Figure 3 . 1 )

 31 Figure 3.21 ΔG H* (kcal.mol -1 ) in different adsorption sites (indicated by arrows) of Ru 55 (C 4 H 9 COO) 14 (H) 14 NP.

Scheme 3 . 4

 34 Scheme 3.4 Synthesis of RuNPs stabilized by octanoic acid in THF. The formed nanoparticle is expected to be covered by octanoates, hydrides and THF as were foreseen in chapter II & section 3.1.

identified (figure 3 .

 3 22 a & b). They show a good dispersion on the grid with a homogeneous spherical morphology, since the RuNPs were highly soluble in THF, no problem in the solvent evaporation process was seen. The mean size of the (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs was observed to be ca. 1.34 ± 0.51 nm (figure 3.22 c).

Figure 3 .

 3 Figure 3.22 TEM micrographies of (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs; (a) general view, scale bar: 100 nm; (b) zoom on the nanosystems, scale bar: 50 nm; (c) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3.23 Experimental FTIR spectrum of (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs and main peaks assignments. Experimental peaks position for free octanoic acid (green bars, C 7 H 15 COOH) and THF (yellow bars) are also indicated. ν: stretching; δ: bending; ρ rocking; s: symmetric; as: asymmetric. Peaks attributed to coordinated THF (blue) are likewise shown. The ν as (COOH) vibrational mode region is highlighted with an orange circle.

Figure 3 .

 3 Figure 3.24 allows to compare the FTIR data of (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs directly prepared in THF (figure 3.24 c) with those of RuNPs synthetized with 0.4 equiv. of ethanoic (figure 3.24 a) and of pentanoic (figure 3.24 b) acids in pentane and then purified by THF washings. The comparative analysis will concern three main zones of the spectra highlighted in blue, orange and green.

Figure 3 .

 3 Figure 3.24 Comparison of experimental FTIR data: (a) Ru x (CH 3 COOH) 0.4 ; (b) Ru x (C 4 H 9 COOH) 0.4 ; (c) (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs. Highlighted regions: (blue) ν (CO); (orange) ν (COO(H)); (green) ν (THF).

. 25 a

 25 ). In the area of the characteristic ether vibration bands, the presence of two twin shifted signals attributed to coordinated THF can be detected for the RuNPs synthetized by pentanoic and octanoic acid (figure 3.25 b). CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 191

Figure 3 .

 3 Figure 3.25 Comparison of experimental FTIR data: (blue) Ru x (CH 3 COOH) 0.4 ; (red) Ru x (C 4 H 9 COOH) 0.4 ; (black) (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs. Zoom in two different regions: (a) ν (CO & COO(H)); (b) ν (THF).

Figure 3 8 )

 38 Figure 3.261 H-NMR (THF-d 8) of (Ru x (C 7 H 15 COOH) 0.4 ) THF (red profile) vs free C 7 H 15 COOH (blue profile). Side products are denoted as "x" and the proton assignation is displayed at the bottom.

Figure 3 .

 3 Figure 3.27 Ru 55 NP optimized models with different coverage values of carboxylic acid entities.

Figure 3 .

 3 Figure 3.28 TEM micrograph of (a) (Ru x (C 7 H 15 COOH) 0.15 ) THF NPs; scale bar: 100 nm; (b) corresponding size histogram of individual -a-RuNPs. TEM micrograph of (c) (Ru x (C 7 H 15 COOH) 0.30 ) THF NPs; scale bar: 50 nm; (d) corresponding size histogram of individual -c-RuNPs.

Figure 3 .

 3 Figure 3.29 Experimental FTIR spectra: (a) (Ru x (C 7 H 15 COOH) 0.15 ) THF ; (b) (Ru x (C 7 H 15 COOH) 0.30 ) THF ;(c) (Ru x (C 7 H 15 COOH) 0.40 ) THF NPs. Three specific vibration regions are highlighted: (blue) ν(CO); (green) ν(COOH); (orange) ν(COO).

Scheme 3 . 5

 35 Scheme 3.5 Ligands interacting with the RuNPs surface for (a) (Ru x (C 7 H 15 COOH) 0.40 ) THF vs (b) (Ru x (C 7 H 15 COOH) 0.15 ) THF .

  section 6.1.3.1). Heterogeneous population of nanobjects including large nanoparticles of different sizes in the range [25 -100 nm] and disparate morphologies (figure 3.30 b) together with big agglomerates and metal pieces of ruthenium at the micrometer scale (figure 3.30 a).

Figure 3 .

 3 Figure 3.30 TEM micrographs of Ru x (C 7 H 15 COOH) 0.10 sample; (a) general view, scale bar: 1000 nm; (b) focus on the nanosystem, scale bar: 500 nm.

  Scheme 3.6 Synthesis of RuNPs in pentane using 0.20 equiv. of octanoic acid. The formed Ru x (C 7 H 15 COOH) 0.20 NPs are expected to be covered by octanoates and hydrides.

  carbon-covered copper grid (see section6.1.3.1). The obtained dry grid was used for TEM and furthermore for HRTEM analyses (vide infra). TEM micrographs (figure 3.31 a & b) show a population of RuNPs that are well-dispersed on the grid. They have a homogeneous morphology similar to round particles with small elongation in one of its axes (spheroidal NPs). The frequency count analysis revealed the presence of RuNPs with a mean size of ca. 1.65 ± 0.65 nm (figure 3.31 c).

Figure 3 .

 3 Figure 3.31 TEM micrographs of Ru x (C 7 H 15 COOH) 0.20 NPs; (a) general view, scale bar: 100 nm; (b) focus on the nanosystems, scale bar: 50 nm; (c) corresponding size histogram of individual RuNPs.

Figure 3 .

 3 Figure 3.32 HRTEM analysis of Ru x (C 7 H 15 COOH) 0.20 NPs; (a) micrographs; (b) FFT (c) Miller pattern.

Figure 3 .

 3 Figure 3.33 (a) WAXS spectrum of Ru x (C 7 H 15 COOH) 0.20 NPs (red profile) compared with Ru hcp pattern (blue profile); (b) RDFs comparison in real space of two different batches of Ru x (C 7 H 15 COOH) 0.20 NPs.

Figure 3 .

 3 Figure 3.34 Experimental FTIR spectrum of Ru x (C 7 H 15 COOH) 0.20 NPs and main peaks assignments. Characteristic peaks of octanoic acid (green bars, C 7 H 15 COOH) and THF (yellow bars) are also indicated. ν: stretching; δ: bending; ρ rocking; s: symmetric; as: asymmetric. Regions corresponding to ν(CO) & ν as (COO) are highlighted in blue and orange respectively.

Figure 3 .

 3 Figure 3.35 presents the 1 H-NMR spectrum recorded for the Ru x (C 7 H 15 COOH) 0.20 NPs (red profile) together with that of free octanoic acid (blue profile). In the spectra, the deuterated solvent signal can be found at ca. 7.16 ppm. Apart from this signal only one extra sharp peak attributed to grease at ca. 0.29 ppm can be observed in the red spectrum (Ru x (C 7 H 15 COOH) 0.20NPs), no other well-defined signal was found.

Figure 3

 3 Figure 3.35 1 H-NMR (benzene-d 6 ); (red) Ru x (C 7 H 15 COOH) 0.20 NPs; (blue) C 7 H 15 COOH.

Figure 3 .36 13 C

 313 Figure 3.36 13 C CP Hahn-MAS NMR spectrum of Ru x (C 7 H 15 COOH) 0.20 NPs dispersed in porous silica. C 7 H 15 COOH peaks (CDCl 3 ) are displayed in bars at the bottom of the figure.

Figure 3 .37 13 C

 313 Figure 3.37 13 C HETCOR MAS NMR of Ru x (C 7 H 15 COOH) 0.20 NPs diluted in porous silica.

Figure 3 .38 DOSY 1 H

 31 Figure 3.38 DOSY 1 H-NMR (C 6 D 6 ) recorded for non-purified Ru x (C 7 H 15 COOH) 0.20 NPs. The different observed curves presented are obtained as a result of the different gradient strength applied.

  1.6 ppm) and [δ -ζ]-CH 2 (ca. 1.1 ppm) of coordinated ligands when comparing with the signals of free octanoic acid. These CHAPTER III Octanoic Acid-Capped RuNPs Roberto González Gómez 220 assignations were made on the basis of the chemical shifts obtained for the maximum height of the signals. However, it can be assumed that all the protons of the octanoic ligands resonate in this region due to the broadness of the signals observed. Given previous FTIR and NMR data, we can assume that the stabilizing ligand is under the form of octanoate. A better look of this diffusion-filtration can be observed in the figure 3.39.

Figure 3 .

 3 Figure 3.39 Diffusion-filtered 1 H-NMR spectrum (C 6 D 6 ) recorded for Ru x (C 7 H 15 COOH) 0.20 NPs. C 7 H 15 COOH protons chemical shifts are represented in green bars at the bottom of the figure.

Scheme 3 . 7

 37 Scheme 3.7 Graphical representation of two types of interacting molecules for Ru x (C 7 H 15 COOH) 0.20 NPs as suggested by DOSY NMR. (D 1 ) Strongly coordinated ligand and (D 2 ) ligand weakly coordinated in fast exchange. By applying the Stokes-Einstein equation to the data extracted from the DOSY analysis, allowed to determine the hydrodynamic radii of the two types of species present in solution (see section 6.1.3.6.1). According to this mathematical relation, the system with the lowest diffusion coefficient (D 1 ) have a hydrodynamic diameter of 3.8 nm and those with the highest diffusion coefficient (D 2 ) presents a hydrodynamic diameter of 1.0 nm.

Scheme 3 . 8

 38 Scheme 3.8 Representation of the surface mapping of Ru x (C 7 H 15 COOH) 0.20 NPs completed by the estimated numbers of each type of ligand per RuNP. (I s ) Strongly coordinated, (I w ) weakly coordinated and (I f ) "free"in exchange.

Figure 3 .

 3 Figure 3.40 NOESY NMR spectrum (C 6 D 6 ) of Ru x (C 7 H 15 COOH) 0.20 NPs.

Figure 3 .

 3 Figure 3.41 Selection of Ru 55 NP optimized structures with different ligand surface coverage (C 7 H 15 COO & H).

  2.6). Again, a phase diagram has been calculated by considering the octanoic acid concentration and hydrogen pressure in equilibrium with the Ru 55 NP metal surface (𝑝 𝐻 2 , [C 7 H 15 COOH]) (figure 3.42).

Figure 3 .

 3 Figure 3.42 Δ a G° (𝒑 𝑯 𝟐 , [C 7 H 15 COOH]) phase diagram for H 2 (gas) and C 7 H 15 COOH (liquid) adsorption on Ru 55 NP at 300 K (pressure in bar, concentration in mol.L -1

[ 10 - 4 -Figure 3 .

 1043 Figure 3.43 More stable [Ru 55 ] NP found at 300 K for Ru x (C 7 H 15 COOH) 0.20 NPs. (Domain 73: Ru 55 (C 7 H 15 COO) 14 (H) 14 ; domain 70: Ru 55 (C 7 H 15 COO) 10 (H) 27 ; domain 68: Ru 55 (C 7 H 15 COO) 8 (H) 25 .

1 H

 1 7 H 15 COOH) 0.20 NPsIn section 3.2.5.3.1, DOSY NMR analysis allowed to determine the ratio between coordinated octanoate ligands and surface ruthenium atoms leading to a value of4,4 Ru surf /octanoate ligand. Given this low quantity of coordinated octanoates at the RuNP surface the question of the saturation of this NP surface arises. It can be assumed that the metal surface is not completely crowded and even if the formed Ru x (C 7 H 15 COOH) 0.20 NPs are well-stabilized, it could host a higher quantity of carboxylates species. With the aim to try answering this question, a complementary solution NMR study combining 1D and 2D NMR experiments ( 1 H, DOSY, NOESY) was performed on Ru x (C 7 H 15 COOH) 0.20 NPs by adding an increasing quantity of ligand in the colloidal solution and recording new NMR data (see section 6.1.3.6). Since the experiments were done in the same setup, the grease presented in the NMR spectrum was taken as internal reference. 05 equiv. of octanoic acid was added and the reaction mixture was sonicated during 30 min before recording the NMR data. This methodology was then pursued by adding step by step 0.05 eq more of ligand in order to get up to 0.10, 0.15 and 0.20 equiv. of added ligand (leading to a series of experiments in the presence of 0.25, 0.30, 0.35, and 0.40 ligand in total) in the NMR tube. Evolution of the NMR signals depending on the quantity of free ligand added was thus studied using as reference points the 1 H, DOSY, NOESY NMR data described in section 3.2.5.3.1 for the starting Ru x (C 7 H 15 COOH) 0.20 NPs. NMR data recorded for each ligand addition are presented in figure3.44. A signal appeared in the region[10.5 -12.5 ppm] where the acidic proton is expected. This signal is very difficult to distinguish for a total quantity of ligand of 0.25 equiv., but it displays a better definition when increasing the ligand content. In the region [0.5 -2.7 ppm] where the signals of the alkyl chain of octanoic acid are expected, the very broad signal visible for the starting RuNPs decreased while increasing the ligand amount. In parallel sharp signals appeared whose positions correspond to the peaks of free octanoic acid.

Figure 3 .44 1 H

 31 Figure 3.441 H-NMR (C 6 D 6 ) spectra of Ru x (C 7 H 15 COOH) 0.20 NPs with different ligand addition. (blue) reference, 0.20 equiv.; (red) + 25 %, 0.25 equiv.; (green) + 50 %, 0.30 equiv.; (purple) + 75 %, 0.35 equiv.; (gray) + 100 %, 0.40 equiv. C 7 H 15 COOH protons chemical shifts are represented in green bars at the bottom of the figure.

  Scheme 3.11 Representation of the evolution of the quantity of I s and I w ligands depending on the quantity of ligand added. The scheme is focus on the RuNPs saturation that was obtained for the Ru x (C 7 H 15 COOH) 0.30 NPs.

3 . 1 )

 31 the RuNPs have similar morphology as the observed for Ru x (C 7 H 15 COOH) 0.20 NPs (figure 3.45 b vs c). The mean size of the Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs (calculated by fast counting) was ca. 1.68 ± 0.41 nm, which is quite similar as the achieved from preformed Ru x (C 7 H 15 COOH) 0.20 NPs (ca. 1.65 nm). As a conclusion, it can be said that the metal component of the RuNPs was not affected by adding extra quantity of ligand.

Figure 3 .

 3 Figure 3.45 TEM micrographs of Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs; (a) general view, scale bar: 200 nm; (b) focus on the nanosystems, scale bar: 50 nm; (c) micrograph of initial Ru x (C 7 H 15 COOH) 0.20 NPs; scale bar: 50 nm.

1 H

 1 6.3). No positive NOE signals were observed for a low addition of extra ligand, even when the NMR indicates the presence of sharp peaks. This can be explained by the fact that the biggest species have a higher weight on the NOE spectra. the last addition of octanoic acid, Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs, at least three different signals that present a positive NOE were found at ca. 2.2, 1.5 and 1.3 ppm. These chemical shifts are similar to those of the α, β and γ protons of the free octanoic acid (figure 3.46 blue signals).

Figure 3 .

 3 Figure 3.46 NOESY-NMR spectrum (C 6 D 6 ) obtained for Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs. Positive NOE is highlighted in green circles.

  CO for 24 h. NMR data recorded on this sample did not show any signal of CO (figure 3.48). This result indicated that the porous silica itself does not adsorb CO, and the probable deposition of CO onto the diluted Ru x (C 7 H 15 COOH) 0.20 NPs can be only performed onto the RuNPs.

Figure 3 .48 13 C

 313 Figure 3.48 13 C MAS NMR spectrum of a sample of porous silica impregnated with octanoic acid after exposure under 1 bar of 13 CO.

Figure 3 .49 13 C

 313 Figure 3.49 13 C MAS NMR spectrum of Ru x (C 7 H 15 COOH) 0.20 NPs dispersed in porous SiO 2 . After exposure under 1 bar of 13 CO for 24 h. Spinning side bands are identified as SSB.

Figure 3 . 1 )

 31 Figure 3.50 ΔG H (kcal.mol -1 ), arrows indicate the adsorption sites of Ru 55 (C 7 H 15 COO) 14 (H) 14 NP.

Figure 4 . 1

 41 Figure 4.1 Representation of the arene reduction pathways: Influence of the MNPs as catalyst in mild conditions.

4-( 3 -

 3 phenylpropyl)pyridine ligand onto the metal surface, as shown by NMR studies, while in the case of the arylphosphines the phenyl groups are not interacting since the ligand coordination takes place through the phosphorous atom. Introduction Roberto González Gómez 261

Figure 4 . 2

 42 Figure 4.2 Expected partial or total reduction of aryl groups in stabilizing ligands of RuNPs.

Scheme 4 . 1

 41 Scheme 4.1 Synthesis of RuNPs stabilized by benzoic acid in THF-d 8 .

Figure 4 .

 4 Figure 4.3

3

 3 Figure 4.3

1 H-NMR (THF-d 8 )

 18 analyses of the decomposition of [Ru(COD)(COT)] under 3 bar H 2 in the presence of 0.2 equiv. of benzoic acid and of the possible formation of RuNPs. On figure 4.4. which is a zoom of the aromatic region of the 1 H-NMR spectrum, the broadness of the benzoic acid signals is more visible as well as the appearance of new peaks that can be attributed to a partial reduction of the aromatic ring, which later on appeared to be completely reduced into cyclohexylmethanol. At the end of the experiment (violet spectrum, 24 h of reaction time) no signals are visible in the spectrum meaning no free ligand is present in solution.

Figure 4 . 4 8 )

 448 Figure 4.4 Zoom of the aromatic region of the 1 H-NMR (THF-d 8 ) spectra provided in figure 4.3.

1 H-

 1 Scheme 4.2 Representation of the ligand exchange studied between C 7 H 15 COOH and C 6 H 5 COOH onto preformed Ru x (C 7 H 15 COOH) 0.20 NPs.

7 .

 7 16 ppm, it was observed the appearance of signals in the range of [6.5 -8.5 ppm] that grew while adding more benzoic acid in the NMR tube. These signals correspond to benzoic acid and their ill-definition and broadness are indicative of an interaction with the RuNPs (figure 4.5 low field). It is worth to say that the presence of this deprotected proton signals indicates the absence of the benzoic acid reduction.

Figure 4 .5 1 H

 41 Figure 4.51 H-NMR (C 6 D 6 ) spectra of Ru x (C 7 H 15 COOH) 0.20 NPs, represented as 0.20 OcAc, after addition of an increasing quantity of benzoic acid. (red) initial RuNPs stabilized with 0.20 equiv. of OcAc; (dark green) 0.20 OcAc + 0.05 equiv. of BAc; (green) 0.20 OcAc + 0.10 equiv. of BAc; (blue) 0.20 OcAc + 0.20 equiv. of BAc; (purple) 0.20 OcAc + 0.30 equiv. of BAc. Chemical shifts of the octanoic acid protons (C 7 H 15 COOH) are presented in green bars at the bottom.

1

 1

Figure 4 .6 Diffusion-filtered 1 H

 41 Figure 4.6 Diffusion-filtered 1 H-NMR spectra (C 6 D 6 ) obtained for Ru x (C 7 H 15 COOH) 0.20 NPs, represented as 0.20 OcAc, during addition of benzoic acid. (red) initial RuNPs stabilized with 0.20 equiv. of OcAc; (dark green) 0.20 OcAc + 0.05 equiv. of BAc; (green) 0.20 OcAc + 0.10 equiv. of BAc; (blue) 0.20 OcAc + 0.20 equiv. of BAc; (purple) 0.20 OcAc + 0.30 equiv. of BAc.

3 . 1 .

 31 Due to technical issues, the surface mapping could be done only for the addition of 0.10, 0.20 and 0.30 equiv. of benzoic acid to the colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 NPs. The studies were performed by integrating the evolution of the octanoates signals (ca. [2.5 -0.75 ppm]) and the benzoic acid peaks (ca. [6.5 -8.3 ppm]).

Figure 4 .

 4 Figure 4.7 provides a view of the surface coverage of the particles after addition of 0.1 equiv. of benzoic acid in comparison with the initial surface coverage for Ru x (C 7 H 15 COOH) 0.20 NPs

Figure 4 . 7

 47 Figure 4.7 Left: Estimated initial surface mapping of Ru x (C 7 H 15 COOH) 0.20 NPs; right: estimated new surface coverage obtained after the ligand exchange with 0.10 equiv. of benzoic acid.

Figure 4 . 8

 48 Figure 4.8 NOESY NMR spectrum (C 6 D 6 ) recorded gathered after addition of 0.05 equiv. of benzoic acid to colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 NPs. The positive NOE is highlighted in green circles.

Figure 4 . 9

 49 Figure 4.9 TEM micrographs of (a) Ru x (C 7 H 15 COOH) 0.20 NPs, scale bar: 50 nm; and (b) Ru x (C 7 H 15 COOH) 0.20 NPs + 0.30 equiv. of BAc, scale bar: 50 nm. Fast NPs frequency count is presented for each sample.

Figure 4 .

 4 Figure 4.10 Representation of the octanoic vs benzoic acid ligand exchange at the RuNPs surface. Possible driving forces: (a) steric hindrance; (b) acidity.

Figure 4 .

 4 Figure 4.11 Theoretical models representing the interaction of carboxylic moieties with the Ru 55 NP over the (001) plane. (a) octanoic acid; (b) benzoic acid; (c) octanoate; (d) benzoate. The E ads (kcal.mol -1

Figure 4 .

 4 Figure 4.12 Ligand exchange reactions between octanoic and benzoic acids onto Ru 55 NP studied by DFT.

Figure 4 .

 4 Figure 4.13 Representation of ligand exchange between octanoic and benzoic acids according to the obtained DFT energies for the studied reactions.

Scheme 4 . 3 1 H

 431 Scheme 4.3 Representation of the ligand exchange reaction between C 7 H 15 COOH and CF 3 COOH at starting from RuNPs sample Ru x (C 7 H 15 COOH) 0.20 NPs + 0.2 equiv. OcAc.

Figure 4 .14 1 H

 41 Figure 4.141 H-NMR (C 6 D 6 ) spectra of initial Ru x (C 7 H 15 COOH) 0.20 NPs, represented as 0.20 equiv. OcAc, and after addition of octanoic and TFA. (blue) initial NPs stabilized with 0.20 equiv. of OcAc; (green) Ru x (C 7 H 15 COOH) 0.20 NPs + 0.20 equiv. of OcAc; (red) Ru x (C 7 H 15 COOH) 0.20 NPs + 0.20 equiv. of OcAc + 0.10 equiv. of TFA. Chemical shifts of the protons of free octanoic acid (C 7 H 15 COOH) are given as green bars at the bottom

The 19 F

 19 -NMR spectrum (figure 4.15) shows a broad signal (ca. 74.0 ppm) attributed to TFA in a strongly interacting mode with the RuNPs. A sharp peak at the same chemical shift as free TFA (ca. 75.6) is also visible. Therefore, it can be assumed that a certain quantity of the 0.10 equiv. of CHAPTER IV Octanoic Acid vs TFA Roberto González Gómez 289 added TFA is coordinated and also that there are TFA molecules which do not interact with the ruthenium surface being present as free or in dynamic exchange. The deconvolution of the 19 F-NMR spectrum indicates a contribution of 74.9 % of the signal for coordinated TFA the rest of the signal (25.1 %) corresponding to free ligand in solution or in dynamic exchange.

Figure 4 .15 19 F

 419 Figure 4.15 19 F-NMR (C 6 D 6 ) spectra of Ru x (C 7 H 15 COOH) 0.20+0.20 NPs after the addition of 0.10 equiv. of TFA. The deconvolution of the spectrum and contribution percentage (%) of the signal are also presented.

2 . 5 . 3 . 1 & 4 . 2 . 2 .

 2531422 Proton DOSY NMR experiments were performed on the Ru x (C 7 H 15 COOH) 0.20+0.20 (CF 3 COOH) 0.10 NPs. As it will be seen, these analyses allowed to complete the surface mapping of the RuNPs surface after addition of 0.10 equiv. of TFA and to determine the ratio of the octanoic vs TFA ligand exchange.The studies were obtained by integrating the evolution of the octanoates signals (ca. [1.8 -0.8] ppm) in DOSY analysis and their contributions were determined. As in previous DOSY NMR experiments, the diffusional attenuation could be fitted with a Stejskal-Tanner equation by using a bi-exponential analysis. This indicated the presence of two types of molecules interacting with the RuNPs surface, namely ligands with strong (D s ) and weak interaction (D w ).

Figure 4 .

 4 Figure 4.16 Representation of the octanoic acid vs trifluoroacetic acid ligand exchange with estimated numbers of each type of ligand surrounding the particles in initial Ru x (C 7 H 15 COOH) 0.20+0.20 NPs and those obtained after addition of 0.10 equiv. of TFA. Ligand strongly attached (I s ), weakly interacting (I w ) and in exchange or free (I f ).

  x (C 7 H 15 COOH) 0.20 NPs and of Ru x (C 7 H 15 COOH) 0.20+ 0.20 NPs (Figure 4.17). Similar sizes were observed for the tree samples of RuNPs (ca. 1.69 nm for Ru x (C 7 H 15 COOH) 0.20+ 0.20 NPs vs 1.65 nm for Ru x (C 7 H 15 COOH) 0.20 NPs).

Figure 4 .

 4 Figure 4.17 TEM micrographs of (a) Ru x (C 7 H 15 COOH) 0.20 NPs, scale bar: 50 nm; (b) Ru x (C 7 H 15 COOH) 0.20+0.20 NPs, scale bar: 50 nm; (c) Ru x (C 7 H 15 COOH) 0.20+0.20 NPs + 0.10 equiv. of TFA, scale bar: 50 nm.

  2.3). The deprotonated species involved in the ligand exchange (octanoate and trifluoroacetate) were deposited onto the same crystalline plane (001) of the Ru 55 NP model (see section 6.2.1) as schematized in figure 4.18. The obtained values are provided in the section appendix B.3 and structural coordinates in the section appendix F.

Figure 4 .

 4 Figure 4.18 Theoretical models used to study the interaction of the three carboxylates with the Ru 55 NP over the (001) plane. (a) octanoate; (b) benzoate; (c) trifluoroacetate. The E ads (kcal.mol -1

5 . 1

 51 Figure 5.1 Example of bipyridine-based ruthenium (II) photosensitizer. [Ru(bpy) 3 ]2+ .

Figure 5 . 2 306 5. 2

 523062 Figure 5.2 Representative diagram of the PS incorporation on preformed RuNPs.

Figure 5 . 3

 53 Figure 5.3 Bipyridine-based ruthenium complexes photosensitizers used for DFT calculations.

Figure 5 . 4

 54 Figure 5.4 Optimized theoretical models for the interaction of PS1 (left) & PS2 (right) molecules with the Ru 55 (CH 3 COO) 2 (H) 2 . The E ads (kcal.mol -1

Figure 5 . 5

 55 Figure 5.5 Optimized theoretical models for the interaction of PS3 (left) & PS4 (right) molecules with Ru 55 (CH 3 COO) 2 (H) 2 NP. The E ads (kcal.mol -1

Figure 5 . 6

 56 Figure 5.6 Optimized theoretical models for the interaction of (a) PS1, (b) PS2 and (c) PS4 molecules with Ru 55 (CH 3 COO) 10 (H) 27 NP and corresponding E ads (kcal.mol -1

Figure 5 . 7

 57 Figure 5.7 Optimized theoretical calculations for the reaction of PS1 and of PS4 with Ru 55 (CH 3 COO) 12 (H) 29 NP.

Figure 5 . 8 1 )

 581 Figure 5.8 Optimized theoretical calculations for the interaction of PS1 with the (a) Ru 55 (CH 3 COO) 10 (H) 27 NP and (b) Ru 55 (CH 3 COO) 14 (H) 31 NP. The E ads (kcal.mol -1) are also presented.

Scheme 5 . 1

 51 Scheme 5.1 Representation of an incorporation of a PS adsorption onto crowded Ru 55 NP. (left) PS1 and (right) PS4 ligand

( 4 Å

 4 beads, Alfa Aesar) into the globe-box. TFA-d[START_REF] Züttel | Hydrogen as a Future Energy Carrier[END_REF] for ligand exchange experiments was acquired from Euriso-top and used right after opening below a continuous argon flow. Silica gel (pore size 60 Å) was purchased from Fluka Analytical, dried by thermal treatment (ca. 590 °C) under vacuum and then stored in the globe-box. Methanol (VWR Chemicals) was purified, dried and degassed by distillation under inert atmosphere, using magnesium as a drying agent previously activated with iodine and stored under argon. Potassium bromide (Sigma-Aldrich) was dried over P 2 O 5 (Sigma-Aldrich) before usage and conserved in the globe-box for FTIR analysis. The other chemicals were employed as received unless otherwise specified.

Figure 6 . 1

 61 Figure 6.1 3D ball representation of [Ru(COD)(COT)] complex.

  3 ▪xH 2 O. Inside a 250 mL Schlenk flask, 3 g (5.8 mmol) of RuCl 3 ▪xH 2 O were dissolved in 30 mL of dried and degassed methanol under vigorous stirring. After, 80 mL (1.53 mol) of purified 1,5-cyclooctadiene were added to the flask under stirring till a homogeneous solution was achieved. Then, 5 g of granular zinc were added (catalyst) to the reaction mixture which was heated till reflux (90 °C) for 3 h under continuous flux of argon.

Figure 6 .2 1 H

 61 Figure 6.2 1 H-NMR of [Ru(COD)(COT)]: (right) C 7 D 8 ; (left) CDCl 3 .

Scheme 6 . 1

 61 Scheme 6.1 General synthesis of RuNPs.

6. 1 . 3

 13 Characterization TechniquesSynthetized ruthenium nanoparticles (RuNPs) were characterized by a combination of different techniques. Size, morphology and crystalline structure of the particles were determined by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and wide-angle X-ray scattering (WAXS). Elemental analysis (EA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Energy-dispersion X-ray (EDX) allowed to get the ratio between metal and organics (ligands) at the RuNPs surface, nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies were used to analyze the surface composition of the nanoparticles. Gas chromatography (GC) was used in order to titrate the quantity of hydrogen atoms (hydrides) present at the surface of the nanoparticles by a home-made titration method (vide infra).6.1.3.1 Transmission Electron Microscopy (TEM), High-Resolution TEM (HRTEM) and Energy-Dispersive X-Ray Spectroscopy (EDX)Transmission electron microscopy analyses were performed at the "Centre de Microcaractérisation Raymond Castaing" in Toulouse, France (UMS-CNRS 3623). Samples were prepared by slow evaporation of a drop of crude concentrated colloidal RuNPs suspension deposited under oxidizing atmosphere (air) onto a holey carbon-covered copper grid. TEM analyses were performed using JEOL JEM 1011 or JEOL JEM 1400 microscope, operating at 100 and 120 kV, respectively with a point of resolution of 0.45 nm. TEM was used as standard tool to determine the shape, morphology and mean size of the ruthenium nanoparticles. Size distributions were built by measuring ca. [400 -300] nanoparticles through a manual counting of several enlarged TEM micrographs. The mean diameters were determined by fitting a Gaussian curve to each statistical size distribution. HRTEM analyses were carried out by Vincent Collière with a JEOL JEM-ARM 200F microscope working at 200 kV with a point of resolution of < 0.19 nm. Fast-Fourier Transform (FFT) treatments of HRTEM micrographies were carried out with the Digital Micrograph software Roberto González Gómez 331 version 1.80.70 in order to determine the crystalline planes, structure and lattice parameter of the synthetized nanoparticles. EDX spectroscopy were performed by Vincent Collière and obtained with a JEOL JEM-ARM 200F (URP) ED microscope, equipped as well as for HRTEM, working at 200 kV. The spectra were evaluated using JED-2300 Analysis Station software taking into account the sensitive factors for the different elements (k-factor corrections). The beam spot sizes depended on the nanoparticle system but in general they ranged between [1 -10] nm. The analyses were obtained for different sections of the characterized grids.

0°<

  < 65° for equidistant s values (𝑠 = 4𝜋 (sin 𝜃 𝜆 )). The reduced data were extracted in order to see the structure-related component of WAXS normalized to a number of atoms corresponding to the nanoparticles size. Radial distribution functions (RDF) were obtained after Fourier transformation of the corrected and reduced intensity functions. Roberto González Gómez 333 6.1.3.6 Liquid Nuclear Magnetic Resonance Solution nuclear magnetic resonance (NMR) at high-resolution were accomplished by Christian Bijani in the "Service de Resonance Magnétique Nucléaire" at the LCC-CNRS, Toulouse, France. Liquid proton ( 1 H-NMR) and fluorine nuclear magnetic resonance ( 19 F-NMR), diffusion-ordered spectroscopy (DOSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments were performed on four different Bruker spectrometers (Avance 400, Avancelll 400, Avance 500 and Avance NEO 600) at 298 K. Preparation of the NMR tubes was carried out under argon atmosphere using deuterated solvents (chlorophorm-d 1 , benzene-d 6 , toluene-d 8 and THF-d 8 )to re-disperse the dried nanoparticles powder.DOSY measurements were performed with a diffusion delay () between [150 -200 ms],

Figure 6 . 3

 63 Figure 6.3 Maximum NOE obtained in NOESY (solid line) and ROESY experiment (dash line) as a function of τ c .

  2), DOSY experiments were performed at r.t. ([20 -25 °C]).

  1.0 nm 55-atom hcp metal ruthenium nanoparticle (Ru 55 ), which is smaller ca. [35.0 -40.0 %] than the approximate mean size of the RuNPs synthetized ([1.5 -1.7 nm]), was utilized as a basis model to perform DFT calculations. The chosen Ru 55 model, designed in a previous published work, has been shown to properly describe the surface properties of ultra-small RuNPs (figure 6.4

Figure 6 . 4

 64 Figure 6.4 Ultra-small Ru 55 model.

Figure 6 . 5

 65 Figure 6.5 Ru 55 hcp-based NP; different surface sites are highlighted.

  Gaussian smearing width () of 0.02 eV. Geometry optimizations were done till the criteria of the residual forces on any direction were less than 0.02 eV.Å -1 . The used supercell size was set to ensure a ca. 16 Å vacuum space between periodic images of the ruthenium cluster (figure6.6). For example, a 27.0 x 27.0 x 27.5 Å large supercell was set up for a Ru 55 (CH 3 COO) 16 H 16 NP whereas a 35.0 x 35.0 x 36.0 Å large supercell was set up for a Ru 55 (C 7 H 15 COO) 14 H 14 NP.

Figure 6 . 6

 66 Figure 6.6 Translational symmetry of the supercell method within periodic-DFT calculations: Orthorombic unitcell (a = 27.0 Å, b = 27.0 Å, c = 27.5 Å) that contains Ru 55 (CH 3 COO) 16 H 16 periodically replicated 3 x 3 x 3.

  10 5 -10 -20 M] for R-COOH in THF and the scope of [10 5 -10 -20 bar] for H 2 . The mapping of the RuNPs surface in Roberto González Gómez 347 for a given Ru 55 NP optimized structure with certain ligand coverage: Ru {4p, 4d, 5s, 5p}; C, N, O and F {ns, np}; H {1s}.

Illustration 2 .

 2 Schémas de RuNPs stabilisées par (a) mélange de MeOH/THF et (b) 4-phénylpyridine.

[ 9 ]

 9 Malgré la diversité des RuNPs reportées dans la littérature, il demeure nécessaire de modifier leur état de surface afin d'améliorer leurs propriétés catalytiques. Les propriétés physiques et chimiques des RuNPs dépendent de leurs caractéristiques structurales telles que leur taille moyenne, leur forme, leur structure cristalline, mais aussi la nature et la quantité des ligands présents à leur surface. Les ligands assurent la stabilité des nanoparticules mais peuvent également influer sur leurs propriétés de surface. Bien que les acides carboxyliques soient largement utilisés comme tensioactifs en synthèse colloïdale, l'adsorption directe d'acides carboxyliques sur les surfaces métalliques de nanoparticules de ruthénium est très peu reportée. Ce manuscrit de doctorat constitue une étude fondamentale amont dans le but de concevoir une nouvelle classe de nanocatalyseurs pour la réaction HE activée par la lumière. Afin de disposer de catalyseurs activables par la lumière du soleil, il est nécessaire d'élaborer des matériaux hybrides combinant des NPs métalliques (ici de Ru) avec des molécules photosensibles (PS) greffées à leur surface, dénotés RuNPs-PS. Par exemple, des complexes polypyridyl du ruthénium présentant des groupements acides carboxyliques comme fonctions d'ancrage peuvent être greffés sur des NPs. Cette stratégie a été précédemment démontrée comme étant un moyen efficace pour atteindre les matériaux hybrides souhaités. Dans cet objectif, nous avons étudié les propriétés de surface de RuNPs stabilisées par des acides carboxyliques comme systèmes modèles. Des ligands acides carboxyliques portant des RESUME DE LA THESE Roberto González Gómez 356 chaînes alkyles de différentes longueurs ont été utilisés comme stabilisants pour la synthèse de RuNPs. Ces RuNPs ont été synthétisées dans des conditions douces selon l'approche organométallique développée au laboratoire (illustration 3) en utilisant les acides éthanoïque, pentanoïque et octanoïque. Cette méthode de synthèse est connue pour conduire, de façon reproductible, à la formation de RuNPs de petites tailles et homogènes ce qui permet de mener des études de caractérisation de leur propriétés de surface très fines. Illustration 3. Schéma général de synthèse des MNPs par approche organométallique.

Illustration 4 .

 4 Modèle de NP Ru 55 basé sur une structure hcp . a) Modèle Ru 55 optimisé stabilisé par la coadsorption des éthanoates et des atomes d'hydrogène ; b) les différents sites de surface construits dans le modèle Ru 55 . Ce manuscrit de thèse comporte cinq chapitres. Après une introduction générale (chapitre 1) qui se termine par la présentation des objectifs fixés, le chapitre 2 rassemble les résultats de l'étude approfondie menée pour la caractérisation théorique et expérimentale de RuNPs stabilisées par 0,4 équivalents molaires (equiv. ; RCOOH/[Ru]) d'acide éthanoïque. La synthèse de ces nanoparticules (illustration 5) a été réalisée en décomposant une solution dans le pentane du précurseur de ruthénium, [Ru(COD)(COT)], sous 3 bar de H 2 à r.t., pendant 30 min. Le fait que l'acide éthanoïque porte une chaîne alkyle très courte rend l'utilisation de ce ligand très pertinente puisqu'ainsi il n'y a pas ou très peu d'influence du groupement alkyle sur la stabilisation des RuNPs, comme on peut l'observer avec des stabilisants portant des chaînes alkyles plus longues. Il est aussi important de souligner la nature du solvant utilisé pour la synthèse des RuNPs (pentane) qui n'est pas connu pour contribuer à la stabilisation des nanoparticules métalliques contrairement au THF par exemple. Ainsi, l'utilisation de l'acide éthanoïque et du pentane constituait déjà un défi de synthèse. Après optimisation des conditions de synthèse, une population homogène de RuNPs (Ru x (CH 3 COOH) 0.4 ) a été obtenue avec un ratio [ligand]/[Ru] de 0,4 equiv. Les analyses TEM et WAXS ont mis en évidence des RuNPs de taille moyenne centrée à ca. 1,5 nm et peu cristallines, avec certaines particules présentant des plans attribuables à la structure cristalline hcp du ruthénium massif (illustration 6). Illustration 6. Analyses de microcopie pour le Ru x (CH 3 COOH) 0,4 NPs. (a) Micrographe de TEM ; échelle graphique 50 nm ; son histogramme de taille est aussi présenté ; b) analyse FFT de HRTEM ; c) structure cristalline des RuNPs. Les propriétés de surface et la réactivité de ces nanoparticules ont été étudiées par deux approches complémentaires, la chimie expérimentale et la chimie théorique. À cette fin, les techniques spectroscopiques, IRFT et RMN (en solution et à l'état solide) ont été utilisées en parallèle de calculs théoriques DFT. Cette combinaison d'outils est apparue très puissante pour obtenir des informations qualitatives mais aussi quantitatives sur l'état de surface des nanoparticules. Tous les résultats obtenus ont convergé vers la coordination du ligand à la surface du ruthénium sous la forme carboxylate (éthanoate), et de préférence en mode bidente formant ainsi un dimétallacycle stable. Ce résultat est en accord avec une faible barrière d'activation pour la dissociation de liaison CH 3 COO-H, ceci quelle que soit la composition de surface des RuNPs. Par ailleurs, les résultats ont montré la co-adsorption d'atomes d'hydrogène à la surface des particules, en quantité plus faible comparativement à d'autres résultats antérieurs sur des RuNPs stabilisées par d'autres ligands (amines phosphines, etc.). Au total, les résultats obtenus convergeaient. Plus précisément, la titration par DFT a montré une composition de surface optimale de ca. [0,4 -0,6] H/Ru Surf et 0,4 CH 3 COO/Ru Surf à 300 K (illustration 7). Ces données sont en bon accord avec les données obtenues par quantification expérimentale (analyse RMN DOSY et titration par hydrogénation d'une oléfine simple), à savoir 0,3 H/Ru Surf et 0,3 CH 3 COO/Ru Surf à r.t. Illustration 7. Structures [Ru 55 ] les plus stables trouvées par calculs DFT pour la modélisation des RuNPs par l'acide éthanoique à 300 K. (a) Ru 55 (CH 3 COO) 16 (H) 16 ; (b) Ru 55 (CH 3 COO) 16 (H) 33 .

Illustration 8 . 1 )

 81 Études structurales sur la structure [Ru 55 ] la plus stable trouvée par DFT. (a) les charges atomiques pMPA atomiques sont indiqués par niveau de couleur ; les charges sont indiquées selon : global (q Ru ), noyau (q Ru c ), atomes de surface (q Ru s ) et ligand (q Hydride , q COO & q Me ). (b) le centre de la bande d est indiqué par un code couleur (eV) ; les ΔG H* sont donnés en kcal.mol et les flèches indiquent les sites d'adsorption. Disposant d'un modèle fiable pour la caractérisation théorique des RuNPs stabilisées par l'acide éthanoïque, l'étude a été étendue à des acides carboxyliques portant des chaines alkyles plus longues, à savoir les acides pentanoïque et octanoïque. Ces résultats sont présentés au chapitre 3.A des fins de comparaison, la synthèse de RuNPs en présence d'acide pentatonique a été menée dans le pentane avec la même quantité de ligand que précédemment (0.4 equiv. molaire).Ceci a conduit à des RuNPs, Ru x (C 4 H 9 COOH) 0,4 , plus solubles dans le pentane et de plus faible taille (ca. 1.1 nm contre 1.5 nm avec l'acide éthanoïque), montrant ainsi l'efficacité de l'acide pentatonique à stabiliser les particules et aussi l'influence de la nature du ligand acide carboxylique sur leurs caractéristiques. Des études RMN en solution ont mis en évidence l'absence de signaux correspondant au ligand libre, indiquant donc que le tout le ligand est en interaction avec la surface des nanoparticules. De plus, le signal correspondant aux protons du groupement méthyle s'est avéré bien visible, indiquant ainsi que la chaîne alkyle du ligand n'est pas repliée vers la surface métallique mais étendue. Par RMN DOSY des signaux larges dans la plage des signaux attendus pour le ligand ont été observés, comme attendu pour la coordination du ligand à la surface des particules. Le diamètre hydrodynamique calculé à partir du coefficient de diffusion mesuré par DOSY s'est avéré en bon accord avec la taille moyenne des RuNPs déterminées par l'analyse TEM.L'analyse FTIR (illustration 9) a permis de confirmer la déprotonation de l'acide pentatonique à la surface des nanoparticules : le signal d'une fraction carboxylate a été observé, mais pas celui correspondant à l'acide éthanoïque (libre ou coordonné). L'IRFT a également mis en évidence la présence de THF (utilisé lors de la purification des particules) et produits de dégradation (CO et polyTHF). Illustration 9. Spectre IRFT de Ru x (C 4 H 9 COOH) 0,4 NPs et indication des principaux pics. Les pics caractéristiques de l'acide pentanoïque (barres vertes, C 4 H 9 COOH) et du THF (barres jaunes) sont également indiqués. Ν : étirement ; δ : flexion ; s : symétrique ; as : asymétrique. Les pics attribués au THF coordonné à la surface des RuNPs sont également indiqués (bleu). Le signal noté -a-est assigné au PolyTHF et celui noté -b-au CO. Un schéma de la composition de surface des RuNPs est également montré. L'énergie d'adsorption calculée pour l'acide pentanoïque sur le modèle de NP Ru 55 (-46,2 kcal.mol -1 ) s'est avérée plus faible d'environ 5 kcal.mol -1 que celle pour l'acide éthanoïque (-51,7 kcal.mol -1 ). Avec une bande d'absorption déplacée vers les bas nombres d'onde pour la forme carboxylate, la spectroscopie IRFT a mis en évidence une rétrocoordination plus élevée de la surface métallique de ruthénium vers la fraction pentanoïque que dans le cas des RuNPs stabilisées par l'éthanoate. La synthèse de particules a ensuite été réalisée en introduisant différentes quantités de ligand acide pentanoïque (de [0,05 à 0,60 equiv.]/[Ru]), afin de trouver des conditions de synthèse RESUME DE LA THESE Roberto González Gómez 363 permettant l'obtention de NPs de taille moyenne proche de celles des RuNPs stabilisées par l'acide éthanoique (ca. 1.5 nm) et au-delà, pouvoir faire une comparaison plus fine de leur état de surface. Ceci a été possible en utilisant un ratio [ligand]/[Ru] de 0.3 équivalent molaire, démontrant la possibilité d'accéder à différentes tailles de NPs en variant la quantité de ligand introduit. La population de particules formées avec ce ratio, Ru x (C 4 H 9 COOH) 0,30 , s'est avérée très homogène et avec une distribution en tailles étroite centrée à 1.5 nm. Comparativement à l'acide éthanoïque, une quantité plus faible d'acide pentanoïque a permis de stabiliser des RuNPs de même taille (0.3 / 0.4 équiv. molaire), ce qui peut s'expliquer par la longueur de la chaine alkyle de l'acide pentanoïque qui permet une meilleure stabilisation. Les NPs Ru x (C 4 H 9 COOH) 0,30 ont été entièrement caractérisées par IRFT et RMN. Les spectres RMN 1 H en solution (illustration 10) ont mis en évidence que des RuNPs de tailles similaires peuvent présenter des taux de couverture de leur surface par le ligand différents. Illustration 10. Spectre 1 H-NMR (THF-d 8 ) des RuNPs ; (profil rouge) Rux(C4H9COOH)0,20 NPs ; (profil bleu) Rux(C4H9COOH)0,30 NPs. Les pics attribués à des sous-produits sont signalés par «x» et les pics de l'acide pentanoïque sont indiqués sous forme de barres. La différence de largeur de bandes entre les 2 systèmes de particules démontre la quantité différente de ligand en interaction. Une composition schématique des RuNPs est également présentée. Les données RMN à l'état solide enregistrées pour les particules Ru x (C 4 H 9 COOH) 0,3 ont confirmé la déprotonation de l'acide pentanoïque et son interaction avec la surface de ruthénium sous forme pentanoate. Sur la base de ce résultat et des informations obtenues antérieurement par un titrage DFT, la quantification des ligands de surface a été réalisée en extrapolant le modèle de NP Ru 55 . Il a été constaté que la structure la plus stable en accord avec les données expérimentales est Ru 55 (C 4 H 9 COO) 14 (H) 14 . Cette structure possède des quantités de ligands carboxylates et d'hydrures inférieures à celles déterminées pour les particules Ru x (CH 3 COOH) 0,4 à savoir Ru 55 (CH 3 COO) 16 (H) 16 (illustration 11). Ce résultat a confirmé le meilleur effet stabilisant de l'acide pentanoïque comparativement à l'acide éthanoïque. Illustration 11. Structures [Ru 55 ] les plus stables obtenues par titration DFT à 300 K. (a) RuNPs stabilisées par l'acide éthanoïque ; Ru 55 (CH 3 COO) 16 (H) 16 ; b) et l'acide pentanoïque ; Ru 55 (C 4 H 9 COO) 14 (H) 14 . L'évaluation théorique de l'intérêt du système de RuNPs le plus stable (Ru 55 (C 4 H 9 COO) 14 (H) 14 ) pour la réaction HE été réalisée. Les résultats obtenus ont indiqué que les RuNPs stabilisés par l'acide pentanoïque s'avèrent plus performantes pour la production d'hydrogène que celles stabilisées par l'acide éthanoïque. En première conclusion, l'augmentation de la longueur de la chaîne alkyle par trois atomes de carbone (acide éthanoïque à pentanoïque) a permis de produire des RuNPs de taille plus faible à un ratio [ligand]/[Ru] plus bas. Les RuNPs formées se sont avérées plus homogènes en taille et forme, leur surface moins encombrée et a priori plus intéressantes pour la réaction catalytique de l'HE. Dans le but de mieux comprendre l'influence de la longueur de la chaîne alkyle sur les propriétés des RuNPs, la synthèse de RuNPs avec un acide carboxylique portant une chaîne alkyle encore plus longue, l'acide octanoïque, a été réalisée. Ces résultats sont présentés dans la seconde partie du chapitre 3. Des synthèses ont été réalisées en utilisant le THF ou le pentane comme solvant. La synthèse de RuNPs en présence de 0.4 equiv. molaires d'acide octanoïque dans le THF a conduit à des RuNPs très stables pour lesquelles des analyses RMN et IRFT ont mis en évidence la présence de ligand libre et de différentes molécules coordonnées (acide octanoïque protoné et déprotoné). Les études DFT sur La détermination des énergies d'adsorption par calculs DFT à partir RESUME DE LA THESE Roberto González Gómez 366 du modèle Ru 55 NP ont montré une plus faible force d'adsorption de l'acide octanoïque y compris lorsque des effets de dispersion ont été considérés. Cependant, une tendance a été observée : plus la longueur de la chaîne alkyle de la molécule adsorbée (carboxylate linéaire), plus son énergie d'adsorption sur la surface du Ru 55 NP est faible (illustration 12). Cela signifie que d'autres facteurs sont probablement impliqués dans la stabilisation des RuNPs, comme le solvant ou la barrière de ligand. Illustration 12. Structures Ru 55 NP optimisées recouvertes de 12 carboxylates (éthanoate, pentanoate ou octanoate) et 12 atomes d'hydrogène. Les énergies moyennes d'adsorption des acides sont indiquées (kcal.mol -1 ).

Illustration 13 . 5 C 7 H

 1357 Spectres IRFT expérimentaux. Deux régions vibratoires sont surlignées : (vert) ν(COOH) ; (orange) ν(COO).Après optimisation, l'introduction de 0.2 equiv. molaire d'acide octanoïque a conduit à la formation d'une population de nanoparticules bien dispersées, homogènes en forme et présentant une taille moyenne de 1.6 nm (Ru x (C 7 H 15 COOH) 0,2 NPs), soit une taille proche de celle des particules étudiées précédemment avec les acides ethanoïque et pentanoïque. Ce résultat a confirmé l'observation faite précédemment avec l'acide pentanoïque comparativement à l'acide éthanoïque, à savoir que l'utilisation d'un acide carboxylique portant une chaine alkyle plus longue permet de diminuer la quantité de ligand à introduire pour obtenir une taille de NPs similaire dans la gamme 1.5-1.7 nm (illustration 14). Ce résultat a donc confirmé l'influence de la nature du ligand et de son encombrement stérique sur le contrôle de la taille des RuNPs. Illustration 14. Images TEM des RuNPs stabilisées par différentes quantités d'acides carboxyliques (acide éthanoïque, pentanoïque or octanoïque). Comparaison du ratio RCOOH/[Ru] utilisé pour l'obtention de RuNPs de taille similaire . Ce système de RuNPs (Ru x (C 7 H 15 COOH) 0,2 NPs) a ensuite été finement caractérisé par différentes techniques expérimentales et théoriques. Les analyses par HRTEM et WAXS ont montré des particules assez bien cristallisées et de structure hcp. Les études RMN et IRFT, ont mis en évidence l'absence d'acide octanoïque libre et la présence d'octanoate. La quantification des octanoates et d'hydrures coordonnés à la surface des Ru x (C 7 H 15 COOH) 0,2 NPs, réalisée par des études de RMN approfondie ( 1 H, DOSY & NOESY) et une analyse catalytique (réduction du norbornène) a conduit à 0,2 octanoates par Ru Surf (21 H/RuNP) et 0,2 hydrures par Ru Surf (23,15 COO/RuNP). Un titrage DFT à partir du modèle Ru 55 NP a indiqué une tendance similaire: hydrures [0,3 -0,6]/Ru Surf et octanoates [0,2 -0,3]/Ru Surf (illustration 15), montrant de nouveau un bon accord entre les données expérimentales et théoriques. La comparaison de ses valeurs avec celles obtenues précédemment pour les deux autres acides (acide pentanoïque : 0,3 H/Ru Surf et 0,3 C 4 H 9 COO/Ru Surf ; acide éthanoïque : [0,4 -0,6] H/Ru Surf et 0,4 CH 3 COO/Ru Surf ) souligne que plus la longueur de la chaîne alkyle de l'acide carboxylique est importante, plus la quantité de ligand nécessaire pour stabiliser des RuNPs de taille similaire est moindre. Illustration 15. Résultats des titrages des RuNPs Ru x (C 7 H 15 COOH) 0,2 . (a) expérimental et (b) quantification théorique des ligands adsorbés. Afin de compléter la cartographie de la surface des RuNPs Ru x (C 7 H 15 COOH) 0,2 , elles ont été exposées à une atmosphère de 13 CO afin de saturer les atomes libres de Ru. Les analyses RMN (illustration 16) menées après cette exposition ont montré que la coordination du CO a lieu principalement sur les sites de surface correspondant aux arrêtes et sommets, ce qui a permis de déduire que la coordination de l'acide octanoïque est sur les faces. Quant à l'évaluation théorique de l'intérêt de ces RuNPs dans leur structure la plus stable (Ru 55 (C 7 H 15 COO) 14 (H) 14 ) pour la réaction HE, les résultats obtenus ont indiqué que l'énergie d'adsorption de l'hydrogène était très élevée sur les plans mais tout à fait appropriée pour les sommets et arêtes (ΔG H* près de 0 kcal.mol -1 ), confirmant la nature des sites d'adsorption libres déterminées par l'adsorption de CO. de Ru x (C 7 H 15 COOH) 0,2 NPs dispersés dans une matrice de SiO 2 poreuse après exposition sous 1 bar de 13

- 1 )

 1 pour différents sites d'adsorption de Ru 55 (C 7 H 15 COO) 14 (H) 14 NP est également indiquée. La comparaison de ces données avec celles obtenues antérieurement pour les RuNPs stabilisées par l'acide éthanoïque (Ru 55 (CH 3 COO) 16 (H) 16 ) et l'acide pentanoïque (Ru 55 (C 4 H 9 COO) 14 (H) 14 ) a permis de conclure que les particules stabilisées par l'acide pentanoïque présentent le meilleur potentiel en tant que catalyseur pour la HER. Ainsi, des RuNPs présentant un taux de couverture de leur surface plus faible, telles que celles obtenues avec l'acide pentanoïque, ne conduisent pas nécessairement au meilleur catalyseur.

1 ) 1 )

 11 photosensibilisateur sur des RuNPs préformées est faisable. Cependant, ces résultats préliminaires doivent être considérés avec prudence en raison de plusieurs variables pouvant affecter l'efficacité de l'échange de ligands, comme la nature des photosensibilisateurs, leur encombrement stérique, l'acidité, le taux de couverture de la surface des NPs, la nature du ligand échangé, la recombinaison possible avec des protons, etc. Davantage de calculs DFT s'avèrent nécessaires pour compléter cette étude. Cependant, les données obtenues indiquent que la stratégie choisie pour ancrer un photosensibilisateur sur des RuNPs préformées peut permettre la formation de nanomatériaux hybrides PS-RuNP. Plus précisément, les informations recueillies font ressortir que la synthèse des nanocatalyseurs hybrides pour le craquage de l'eau peut être facilitée par l'utilisation d'un photosensibilisateur du type PS4 et d'un système de nanoparticules dont la surface est moyennement saturée. Compte tenu de ces conclusions, les RuNPs stabilisées par 0,3 equiv. d'acide pentanoïque apparaissent comme étant celles à tester en premier dans une réaction d'échange avec le PS4.

B. 2

 2 Adsorption of Octanoate onto Hydrogenated and Bare Ru 55 NP

  2.23 DIFFUSIONAL ATTENUATION OF THE [1.9 -2.2 PPM] AREA FOR RUX(CH3COOH)0.4 NPS DISPERSED IN THF-D 8 AT R.T. DATA WERE ANALYZED WITH A BI-EXPONENTIAL LEAST-SQUARE FITTING. ..............................................................................................................................................................................................................FIGURE 2.24 THEORETICAL MODELS USED FOR STUDYING THE ETHANOIC ACID INTERACTION WITH (A) RU55 NP; MODEL 1 & (B) RU55(CH3COO)15H32 NP; MODEL 2. THE FACETING OF THE SURFACE IS HIGHLIGHTED WITH TRANSLUCENT GRAY PLANES. .......................................................................................................................................................FIGURE 2.25 ENERGY PROFILE OF THE CH3COO-H BOND DISSOCIATION. BLACK PROFILE: O-H ACTIVATION ON THE RU55 NP (MODEL 1); RED PROFILE: O-H ACTIVATION ON THE RU55(CH3COO)15H32 NP (MODEL 2). GEOMETRIES ARE SHOWN FOR THE MODEL 1, SIMILAR PARAMETERS WERE FOUND IN MODEL 2. ENERGIES ARE GIVEN IN KCAL.MOL

	-1 . SOME

CHARACTERISTIC BOND LENGTHS ARE ALSO GIVEN, IN Å (SAME COLOR CONVENTION AS THE ENERGY PROFILES). .......................................................................................

FIGURE 2.26 13 C CP HAHN-MAS NMR OF RUX(CH3COOH)0.4 NPS DILUTED IN POROUS SILICA. ..................................................................................................................

FIGURE 2.27 DFT MEAN CHEMICAL SHIFT OF THE CARBOXYLIC CARBON ATOMS IN THE ETHANOIC ACID DIMER. ...................................................................................................

FIGURE 2.28 METHYL CARBON DFT CHEMICAL SHIFT OF THE ETHANOIC MOIETIES INTERACTING WITH [RU6] NANOCLUSTER. DIFFERENT COORDINATION MODES (A) CH3COOH; Σ CARBON, Μ, (B) CH3COO; Μ, (C) CH3COO; Η & (D) CH3COOH; Η. ..........................................................................................................................................................

FIGURE 2.29 CARBOXYLIC CARBON DFT CHEMICAL SHIFT OF THE CARBOXYLIC MOIETIES FREE AND INTERACTING WITH [RU6] NANOCLUSTER. DIFFERENT COORDINATION MODES (A) CH3COO;

  PHASE DIAGRAM FOR H2 (GAS) AND CH3COOH (LIQUID) ADSORPTION ON RU55 NP AT 200 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L 2.38 ADDITIONAL STABLE [RU55] CLUSTERS FOUND AT 200 K. (DOMAIN 41: RU55(CH3COO)16(H)33; DOMAIN 35: RU55(CH3COO)12(H)65). ...........................................FIGURE 2.39 ΔAG° (𝒑𝑯𝟐, [CH3COOH]) PHASE DIAGRAM FOR H2 (GAS) AND CH3COOH (LIQUID) ADSORPTION ON RU55 NP AT 450 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L ................................................................................................................................................................................................................................. THF). .................................................................................................................................................FIGURE 2.43 ΔAG° (𝒑𝑯𝟐, [THF]) PHASE DIAGRAM FOR H2 (GAS) AND THF (LIQUID) ADSORPTION ON RU55 NP AT 300 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L 2.47 ATOM D-BAND CENTER IS SHOWN AS COLOR MAP (SCALE IN EV) FOR (A) RU55(CH3COO)16(H)16, (B) RU55(CH3COO)(H)54 AND (C) RU55. THE ΔGH* ARE GIVEN (KCAL.MOL AND THE ARROWS INDICATE THE ADSORPTION SITES. THE SURFACE, CORE AND TOTAL AVERAGE D-BAND CENTER VALUES ARE ALSO PRESENTED (EV). ...................................... FIGURE 3.1 HRTEM IMAGES OF (A) FCC AND (B) HCP RUNPS. INSETS OF DECAHEDRAL STRUCTURE AND ILLUSTRATION OF HCP LATTICE ON THE (100) DIRECTION, RESPECTIVELY; SCALES BAR 1.0 NM. [92] ................................................................................................................................................................................................................... FIGURE 3.2 RU55 NP MODEL STABILIZED BY (A) PENTANOIC ACID AND (B) OCTANOIC ACID. .......................................................................................................................... FIGURE 3.3 TEM MICROGRAPHS OF RUX(C4H9COOH)0.4 NPS; (A) SELF-ORGANIZED NPS DUE TO SOLVENT EVAPORATION; SCALE BAR: 500 NM; (B) ULTRA-SMALL RUNPS; SCALE BAR: 50 NM; (C) SIZE HISTOGRAM OF INDIVIDUAL RUNPS. .................................................................................................................................................................. RED) C4H9COOH............................................................................................................................. NPS. ......................................................................................................... FIGURE 3.7 EXPERIMENTAL FTIR SPECTRUM OF RUX(C4H9COOH)0.4 NPS AND MAIN PEAKS ASSIGNMENTS. EXPERIMENTAL CHARACTERISTIC PEAKS OF PENTANOIC ACID (GREEN BARS, C4H9COOH) AND THF (YELLOW BARS) ARE ALSO INDICATED. Ν: STRETCHING; Δ: BENDING; S: SYMMETRIC; AS: ASYMMETRIC. PEAKS ATTRIBUTED FOR COORDINATED THF AT THE RUNPS SURFACE ARE LIKEWISE SHOWN (BLUE). ..................................................................................................................................................................... FIGURE 3.8 TEM MICROGRAPHS OF RUX(C4H9COOH)0.05 NPS; (A) & (B) AGGLOMERATION OF PARTICLES; SCALE BAR: 50 NM & 500 NM, RESPECTIVELY. .......................................FIGURE 3.9 (A) TEM MICROGRAPH OF RUX(C4H9COOH)0.05 NPS; SCALE BAR: 50 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ............................................

	-1 ). -1 ). FIGURE 2.40 ADDITIONAL STABLE [RU55] CLUSTERS FOUND AT 450 K. (DOMAIN 27: RU55(CH3COO)10(H)10; DOMAIN 1: RU55; DOMAIN 2: RU55(H)17; DOMAIN 3: RU55(H)53). ........ FIGURE 2.41 TEM MICROGRAPHS OF RUX(THF)Y NPS; (A) RU AGGLOMERATES; SCALE BAR: 200 NM; (B) RUNPS; SCALE BAR: 50 NM; (C) SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ...... FIGURE 3.4 RU55 NP MODELS WITH A HIGH COVERAGE VALUE OF CARBOXYLATE AND HYDRIDES ENTITIES; MODEL 1: RU55(CH3COO)12(H)12; MODEL II RU55(C4H9COO)12(H)12. ......... FIGURE 2.42 OPTIMIZED GEOMETRY OF RU55(CH3COO)15(H)32(-1 ) FIGURE 3.5 1 H-NMR (THF-D 8 ); (BLUE) RUX(C4H9COOH)0.4 NPS; (FIGURE 3.6 DIFFUSION-FILTERED DOSY 1 H-NMR (THF-D 8 ) SPECTRUM OF RUX(C4H9COOH)0.4

2.33 EXPERIMENTAL FTIR SPECTRUM OF RUX(CH3COOH)0.4 NPS AND THEORETICAL HARMONIC FREQUENCIES CALCULATED FOR MODEL 2 CH3COO*, H* (BLUE: RU-H MODES; RED: RU-ETHANOTE MODES). THE SIGNALS OF CH3COONA ARE ALSO SHOWN. ............................................................................................................................

FIGURE 2.34 PROGRESSIVE METHODOLOGY APPLIED TO OPTIMIZE RU55 NP STRUCTURES WITH DIFFERENT LIGAND (H & CH3COOH) COVERAGES. ...................................................

FIGURE 2.35 ΔAG° (𝑝𝐻2, [CH3COOH]) PHASE DIAGRAM FOR H2 (GAS) AND CH3COOH (LIQUID) ADSORPTION ON RU55 NP AT 300 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L -1 ). ..................................................................................................................................................................................................................................

FIGURE 2.36 MOST STABLE [RU55] STRUCTURES IN EACH DOMAIN. (DOMAIN 39: RU55(CH3COO)16(H)16; DOMAIN 40: RU55(CH3COO)16(H)25; DOMAIN 19: RU55(CH3COO)4(H)74; DOMAIN 37: RU55(CH3COO)14(H)14; DOMAIN 3: RU55(H)35; DOMAIN 7: RU55(CH3COO)(H)54; DOMAIN 8: RU55(CH3COO)(H)71; DOMAIN 5: RU55(H)70). ....................

FIGURE 2.37 ΔAG° (𝒑𝑯𝟐, [CH3COOH]) .................................................................................................................................................................................................................................. FIGURE .-1 ). ............... FIGURE 2.44 MORE STABLE [RU55] CLUSTERS FOUND AT 300 K. (DOMAIN 46: RU55(THF)(H)53; DOMAIN 49: RU55(THF)2(H)53; DOMAIN 52: RU55(THF)3(H)53). .........................

FIGURE 2.45 PROJECTED COHP & DOS PROFILES FOR RUX(CH3COO)16(H)33 NP MODEL. DASHED RED LINE AND DOTTED RED LINE ON THE PDOS PROFILE: D-BAND CENTER OF SURFACE AND CORE RU ATOMS, RESPECTIVELY; BROWN LINE: FERMI ENERGY. THE BACKDONATION OBSERVED IS ALSO HIGHLIGHTED. .....................................................................

FIGURE 2.46 ATOMIC PMPA CHARGES SHOWN AS COLOR MAPS. (A) RU55; (B) RU55(H)17; (C) RU55(CH3COO)16(H)33. THE CHARGE SCALE IS SHOWN ON THE LEFT. CHARGES ARE ALSO SHOWN: GLOBAL (𝑞𝑅𝑢), CORE (𝑞𝑅𝑢𝑐), SURFACE RUTHENIUM ATOMS (𝑞𝑅𝑢𝑠) AND LIGAND (𝑞𝐻𝑦𝑑𝑟𝑖𝑑𝑒, 𝑞𝐶𝑂𝑂 & 𝑞𝑀𝑒). ............................................................ FIGURE FIGURE 3.10 (A) TEM MICROGRAPH OF RUX(C4H9COOH)0.20 NPS; SCALE BAR: 50 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ..........................................

FIGURE 3.11 (A) TEM MICROGRAPH OF RUX(C4H9COOH)0.30 NPS; SCALE BAR: 50 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ..........................................

FIGURE 3.12 (A) TEM MICROGRAPH OF RUX(C4H9COOH)0.50 NPS; SCALE BAR: 50 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ..........................................

FIGURE 3. 13 TEM MICROGRAPH OF RUX(C4H9COOH)0.60 NPS; SCALE BAR: 50 NM; (B) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ...............................................

FIGURE 3.14 1 H-NMR (THF-D 8 ) OF RUNPS; (1) RUX(C4H9COOH)0.05; (2) RUX(C4H9COOH)0.20; (3) RUX(C4H9COOH)0.30; (4) RUX(C4H9COOH)0.40; (5) RUX(C4H9COOH)0.50; (6) RUX(C4H9COOH)0.60. PEAKS ATTRIBUTED TO SIDE PRODUCTS ARE DENOTED WITH AN "X" AND THE SIGNALS FOR PENTANOIC ACID PEAKS ARE DISPLAYED IN BARS AT THE BOTTOM OF THE FIGURE. THE SIGNAL SURROUNDED BY AN ORANGE CIRCLE CORRESPONDS TO FREE LIGAND. .........................................................................................................

FIGURE 3.15 1 H-NMR (THF-D 8 ) OF RUNPS; (GROUP 1, BROWN PROFILE), RUX(C4H9COOH)0.05; (GROUP 2, GREEN PROFILE), RUX(C4H9COOH)0.30; (GROUP 3, PURPLE PROFILE), RUX(C4H9COOH)0.60. PEAKS ATTRIBUTED TO SIDE PRODUCTS ARE DENOTED WITH AN "X" AND THOSE OF PENTANOIC ACID ARE DISPLAYED IN BARS AT THE BOTTOM OF THE FIGURE.

  3.31 TEM MICROGRAPHS OF RUX(C7H15COOH)0.20 NPS; (A) GENERAL VIEW, SCALE BAR: 100 NM; (B) FOCUS ON THE NANOSYSTEMS, SCALE BAR: 50 NM; (C) CORRESPONDING SIZE HISTOGRAM OF INDIVIDUAL RUNPS. ................................................................................................................................................................................... FIGURE 3.32 HRTEM ANALYSIS OF RUX(C7H15COOH)0.20 NPS; (A) MICROGRAPHS; (B) FFT (C) MILLER PATTERN. .........................................................................................FIGURE 3.33 (A) WAXS SPECTRUM OF RUX(C7H15COOH)0.20 NPS (RED PROFILE) COMPARED WITH RU HCP PATTERN (BLUE PROFILE); (B) RDFS COMPARISON IN REAL SPACE OF TWO DIFFERENT BATCHES OF RUX(C7H15COOH)0.20 NPS. .............................................................................................................................................................. FIGURE 3.34 EXPERIMENTAL FTIR SPECTRUM OF RUX(C7H15COOH)0.20 NPS AND MAIN PEAKS ASSIGNMENTS. CHARACTERISTIC PEAKS OF OCTANOIC ACID (GREEN BARS, C7H15COOH) AND THF (YELLOW BARS) ARE ALSO INDICATED. Ν: STRETCHING; Δ: BENDING; Ρ ROCKING; S: SYMMETRIC; AS: ASYMMETRIC. REGIONS CORRESPONDING TO Ν(CO) & ΝAS(COO) ARE HIGHLIGHTED IN BLUE AND ORANGE RESPECTIVELY. ................................................................................................................................................................. BLUE) C7H15COOH. ................................................................................................................ MAS NMR SPECTRUM OF RUX(C7H15COOH)0.20 NPS DISPERSED IN POROUS SILICA. C7H15COOH PEAKS (CDCL3) ARE DISPLAYED IN BARS AT THE BOTTOM OF THE FIGURE. .................................................................................................................................................................................................................. NMR OF RUX(C7H15COOH)0.20 NPS DILUTED IN POROUS SILICA. .............................................................................................................FIGURE 3.38 DOSY 1 H-NMR (C6D6) RECORDED FOR NON-PURIFIED RUX(C7H15COOH)0.20 NPS. THE DIFFERENT OBSERVED CURVES PRESENTED ARE OBTAINED AS A RESULT OF THE DIFFERENT GRADIENT STRENGTH APPLIED. ............................................................................................................................................................................. FIGURE 3.39 DIFFUSION-FILTERED 1 H-NMR SPECTRUM (C6D6) RECORDED FOR RUX(C7H15COOH)0.20 NPS. C7H15COOH PROTONS CHEMICAL SHIFTS ARE REPRESENTED IN GREEN BARS AT

	FIGURE 3.35 ); (RED) RUX(C7H15COOH)0.20 NPS; (FIGURE 3.36 1 H-NMR (BENZENE-D 6 13 C CP HAHN-FIGURE 3.37 13 C HETCOR MAS

3.30 TEM MICROGRAPHS OF RUX(C7H15COOH)0.10 SAMPLE; (A) GENERAL VIEW, SCALE BAR: 1000 NM; (B) FOCUS ON THE NANOSYSTEM, SCALE BAR: 500 NM. ....................

FIGURE THE BOTTOM OF THE FIGURE. .............................................................................................................................................................................................

FIGURE 3.40 NOESY NMR SPECTRUM (C6D6) OF RUX(C7H15COOH)0.20 NPS. ......................................................................................................................................

FIGURE 3.41 SELECTION OF RU55 NP OPTIMIZED STRUCTURES WITH DIFFERENT LIGAND SURFACE COVERAGE (C7H15COO & H). .......................................................................... FIGURE 3.42 ΔAG° (𝒑𝑯𝟐, [C7H15COOH]) PHASE DIAGRAM FOR H2 (GAS) AND C7H15COOH (LIQUID) ADSORPTION ON RU55 NP AT 300 K (PRESSURE IN BAR, CONCENTRATION IN MOL.L -1 ). ...............................................................................................................................................................................................................................

FIGURE 3.43 MORE STABLE [RU55] NP FOUND AT 300 K FOR RUX(C7H15COOH)0.20 NPS. (DOMAIN 73: RU55(C7H15COO)14(H)14; DOMAIN 70: RU55(C7H15COO)10(H)27; DOMAIN 68: RU55(C7H15COO)8(H)25. ................................................................................................................................................................................................

FIGURE 3.44

  SPECTRA OF RUX(C7H15COOH)0.20 NPS, REPRESENTED AS 0.20 OCAC, AFTER ADDITION OF AN INCREASING QUANTITY OF BENZOIC ACID. (RED) INITIAL RUNPS STABILIZED WITH 0.20 EQUIV. OF OCAC; (DARK GREEN) 0.20 OCAC + 0.05 EQUIV. OF BAC; (GREEN) 0.20 OCAC + 0.10 EQUIV. OF BAC; (BLUE) 0.20 OCAC + 0.20 EQUIV. OF BAC; (PURPLE) 0.20 OCAC + 0.30 EQUIV. OF BAC. CHEMICAL SHIFTS OF THE OCTANOIC ACID PROTONS (C7H15COOH) ARE PRESENTED IN GREEN BARS AT THE BOTTOM. ........ PURPLE) 0.20 OCAC + 0.30 EQUIV. OF BAC..................................................................................................................................................FIGURE 4.7 LEFT: ESTIMATED INITIAL SURFACE MAPPING OF RUX(C7H15COOH)0.20 NPS; RIGHT: ESTIMATED NEW SURFACE COVERAGE OBTAINED AFTER THE LIGAND EXCHANGE WITH 0.10 EQUIV. OF BENZOIC ACID................................................................................................................................................................................................... 4.11 THEORETICAL MODELS REPRESENTING THE INTERACTION OF CARBOXYLIC MOIETIES WITH THE RU55 NP OVER THE (001) PLANE. (A) OCTANOIC ACID; (B) BENZOIC ACID; (C) OCTANOATE; (D) BENZOATE. THE EADS (KCAL.MOL -1 ) ARE ALSO PRESENTED....................................................................................................................................FIGURE 4.12 LIGAND EXCHANGE REACTIONS BETWEEN OCTANOIC AND BENZOIC ACIDS ONTO RU55 NP STUDIED BY DFT. ....................................................................................FIGURE 4.13 REPRESENTATION OF LIGAND EXCHANGE BETWEEN OCTANOIC AND BENZOIC ACIDS ACCORDING TO THE OBTAINED DFT ENERGIES FOR THE STUDIED REACTIONS. .................. SPECTRA OF INITIAL RUX(C7H15COOH)0.20 NPS, REPRESENTED AS 0.20 EQUIV. OCAC, AND AFTER ADDITION OF OCTANOIC AND TFA. (BLUE) INITIAL NPS STABILIZED WITH 0.20 EQUIV. OF OCAC; (GREEN) RUX(C7H15COOH)0.20 NPS + 0.20 EQUIV. OF OCAC; (RED) RUX(C7H15COOH)0.20 NPS + 0.20 EQUIV. OF OCAC + 0.10 EQUIV. OF TFA. CHEMICAL SHIFTS OF THE PROTONS OF FREE OCTANOIC ACID (C7H15COOH) ARE GIVEN AS GREEN BARS AT THE BOTTOM ............................................................. SPECTRA OF RUX(C7H15COOH)0.20+0.20 NPS AFTER THE ADDITION OF 0.10 EQUIV. OF TFA. THE DECONVOLUTION OF THE SPECTRUM AND CONTRIBUTION PERCENTAGE (%) OF THE SIGNAL ARE ALSO PRESENTED. ...........................................................................................................................................................FIGURE 4.16 REPRESENTATION OF THE OCTANOIC ACID VS TRIFLUOROACETIC ACID LIGAND EXCHANGE WITH ESTIMATED NUMBERS OF EACH TYPE OF LIGAND SURROUNDING THE PARTICLES IN INITIAL RUX(C7H15COOH)0.20+0.20 NPS AND THOSE OBTAINED AFTER ADDITION OF 0.10 EQUIV. OF TFA. LIGAND STRONGLY ATTACHED (IS), WEAKLY INTERACTING (IW) AND IN EXCHANGE OR FREE (IF). ...................................................................................................................................................................................................FIGURE 4.17 TEM MICROGRAPHS OF (A) RUX(C7H15COOH)0.20 NPS, SCALE BAR: 50 NM; (B) RUX(C7H15COOH)0.20+0.20 NPS, SCALE BAR: 50 NM; (C) RUX(C7H15COOH)0.20+0.20 NPS + 0.10 EQUIV. OF TFA, SCALE BAR: 50 NM. ............................................................................................................................................................................FIGURE 4.18 THEORETICAL MODELS USED TO STUDY THE INTERACTION OF THE THREE CARBOXYLATES WITH THE RU55 NP OVER THE (001) PLANE. (A) OCTANOATE; (B) BENZOATE; (C)

	FIGURE 4.5 H-NMR (C6D6) FIGURE 4.6 DIFFUSION-FILTERED 1 RUNPS STABILIZED WITH 0.20 EQUIV. OF OCAC; (DARK GREEN) 0.20 OCAC + 0.05 EQUIV. OF BAC; (GREEN) 0.20 OCAC + 0.10 EQUIV. OF BAC; (BLUE) 0.20 OCAC + 0.20 1 H-NMR SPECTRA (C6D6) OBTAINED FOR RUX(C7H15COOH)0.20 NPS, REPRESENTED AS 0.20 OCAC, DURING ADDITION OF BENZOIC ACID. (RED) INITIAL EQUIV. OF BAC; (FIGURE 4.14 1 H-NMR (C6D6) FIGURE 4.15 19 F-NMR (C6D6)

3.48 13 C MAS NMR SPECTRUM OF A SAMPLE OF POROUS SILICA IMPREGNATED WITH OCTANOIC ACID AFTER EXPOSURE UNDER 1 BAR OF 13 CO. ..........................................

FIGURE 3.49 13 C MAS NMR SPECTRUM OF RUX(C7H15COOH)0.20 NPS DISPERSED IN POROUS SIO2. AFTER EXPOSURE UNDER 1 BAR OF 13 CO FOR 24 H. SPINNING SIDE BANDS ARE IDENTIFIED AS SSB. ......................................................................................................................................................................................................... FIGURE 3.50 ΔGH (KCAL.MOL -1 ), ARROWS INDICATE THE ADSORPTION SITES OF RU55(C7H15COO)14(H)14 NP. ...............................................................................................

FIGURE 4.1 REPRESENTATION OF THE ARENE REDUCTION PATHWAYS: INFLUENCE OF THE MNPS AS CATALYST IN MILD CONDITIONS. ......................................................................

FIGURE 4.2 EXPECTED PARTIAL OR TOTAL REDUCTION OF ARYL GROUPS IN STABILIZING LIGANDS OF RUNPS......................................................................................................

FIGURE 4.3 1 H-NMR (THF-D 8 ) ANALYSES OF THE DECOMPOSITION OF [RU(COD)(COT)] UNDER 3 BAR H2 IN THE PRESENCE OF 0.2 EQUIV. OF BENZOIC ACID AND OF THE POSSIBLE FORMATION OF RUNPS....................................................................................................................................................................................................

FIGURE 4.4 ZOOM OF THE AROMATIC REGION OF THE 1 H-NMR (THF-D 8 ) SPECTRA PROVIDED IN FIGURE 4.3. .................................................................................................

FIGURE 4.8 NOESY NMR SPECTRUM (C6D6) RECORDED GATHERED AFTER ADDITION OF 0.05 EQUIV. OF BENZOIC ACID TO COLLOIDAL SUSPENSION OF RUX(C7H15COOH)0.20 NPS. THE POSITIVE NOE IS HIGHLIGHTED IN GREEN CIRCLES. ..................................................................................................................................................................

FIGURE 4.9 TEM MICROGRAPHS OF (A) RUX(C7H15COOH)0.20 NPS, SCALE BAR: 50 NM; AND (B) RUX(C7H15COOH)0.20 NPS + 0.30 EQUIV. OF BAC, SCALE BAR: 50 NM. FAST NPS FREQUENCY COUNT IS PRESENTED FOR EACH SAMPLE. ..............................................................................................................................................................

FIGURE 4.10 REPRESENTATION OF THE OCTANOIC VS BENZOIC ACID LIGAND EXCHANGE AT THE RUNPS SURFACE. POSSIBLE DRIVING FORCES: (A) STERIC HINDRANCE; (B) ACIDITY. ...........

FIGURE TRIFLUOROACETATE. THE EADS (KCAL.MOL -1 ) ARE GIVEN FOR EACH CASE. ......................................................................................................................................

FIGURE 5.1 EXAMPLE OF BIPYRIDINE-BASED RUTHENIUM (II) PHOTOSENSITIZER. [RU(BPY)3] 2+ . ..................................................................................................................... FIGURE 5.2 REPRESENTATIVE DIAGRAM OF THE PS INCORPORATION ON PREFORMED RUNPS. ...................................................................................................................... FIGURE 5.3 BIPYRIDINE-BASED RUTHENIUM COMPLEXES PHOTOSENSITIZERS USED FOR DFT CALCULATIONS...................................................................................................... FIGURE 5.4 OPTIMIZED THEORETICAL MODELS FOR THE INTERACTION OF PS1 (LEFT) & PS2 (RIGHT) MOLECULES WITH THE RU55(CH3COO)2(H)2. THE EADS (KCAL.MOL -1 ) ARE ALSO PRESENTED. ...................................................................................................................................................................................................................

TABLE 1 .

 1 1 CLOSE-PACKED MAGIC NUMBER CLUSTERS. THE REST OF THE METAL SURFACE ATOMS HIGHLIGHTED IN BLUE ARE LOCATED IN THE NP FACES. ...............................................

TABLE 1 .

 1 2 EXPERIMENTAL AND THEORETICAL TECHNIQUES FOR DETERMINING RUNPS PROPERTIES. .................................................................................................................

TABLE 2 .

 2 1 NUMBER OF ATOMS FOR METAL NANOPARTICLE OF 1.0 AND 2.0 NM IN SIZE FOLLOWING THEIR TYPICAL CRYSTALLINE STRUCTURE. ............................................................

TABLE 2 .

 2 2 EDX ANALYSIS FOR ELEMENT QUANTIFICATION OF OXYGEN & RUTHENIUM RATIO IN COMPARISON WITH THE EXPERIMENTAL SYNTHESIS RELATION FOR RUX(CH3COOH)0.2 NPS. .

TABLE 2 .

 2 3 EDX ANALYSIS FOR ELEMENT QUANTIFICATION OF OXYGEN & RUTHENIUM RATIO RATIO IN COMPARISON WITH THE EXPERIMENTAL SYNTHESIS RELATION FOR RUX(CH3COOH)0.4

NPS. .............................................................................................................................................................................................................................

TABLE 2 .

 2 4 OPTIMIZED STRUCTURES USED FOR THE DFT SURFACE TITRATION. THE TOTAL NUMBER AND COVERAGE RATIO OF COORDINATED LIGANDS ARE ALSO SHOWN WITH THE

CORRESPONDING DFT ENERGY (EV)

.

(A) NUMBER OF HYDRIDES THAT COME FROM THE DISSOCIATIVE ADSORPTION OF H2; (B) TOTAL NUMBER OF HYDRIDES I.E. THAT COMES FROM A AND FROM THE CH3COO-H BOND DISSOCIATION. ................................................................................................................................................................. TABLE 2.5 OPTIMIZED STRUCTURES USED FOR THE (𝒑𝑯𝟐, [THF]) PHASE DIAGRAM. LIGAND COVERAGE RATIOS ARE ALSO SHOWN WITH THE CORRESPONDING DFT ENERGY (EV). (A) NUMBER OF HYDRIDES THAT COME FROM THE DISSOCIATIVE ADSORPTION OF H2. ....................................................................................................................................... TABLE 3.1 SWEEP OF PENTANOIC ACID MOLAR EQUIVALENTS USED FOR THE SYNTHESIS OF RUNPS. * PREVIOUSLY DESCRIBED. ............................................................................. TABLE 3.2 SCOPE OF PENTANOIC ACID QUANTITY USED FOR THE RUNPS SYNTHESIS WITH THEIR CORRESPONDING MEAN SIZE AND SIZE DISPERSION OBTAINED BY TEM ANALYSES. ............ TABLE 3.3 DIFFERENT GROUPS FOUND BY SWEEPING THE PENTANOIC ACID CONCENTRATION FOR THE RUNPS SYNTHESIS. ................................................................................... TABLE 3.4 DOSY ANALYSES PERFORMED ON A SCOPE OF RUNPS STABILIZED BY DIFFERENT QUANTITY OF PENTANOIC ACID WITH THEIR CORRESPONDING DIFFUSION COEFFICIENTS, CALCULATED HYDRODYNAMIC DIAMETER AND ESTIMATED SIZE RUNPS SPECIES. .............................................................................................................................................. TABLE 3.5 COMPARISON BETWEEN THE DATA OBTAINED BY TEM STUDIES VS DOSY ANALYSES FOR RUNPS SYNTHETIZED WITH DIFFERENT QUANTITIES OF PENTANOIC ACID. .................. TABLE 3.6 ELEMENTAL ANALYSIS OF RUX(C4H9COOH)0.3 NPS ............................................................................................................................................................. TABLE 3.7 OPTIMIZED STRUCTURES USED FOR THE RUX(C4H9COOH)0.3 DFT SURFACE TITRATION. THE TOTAL NUMBER AND COVERAGE RATIO OF COORDINATED LIGANDS ARE ALSO GIVEN WITH ITS CORRESPONDING DFT ENERGY (EV). (A) NUMBER OF HYDRIDES THAT COME FROM THE DISSOCIATIVE ADSORPTION OF H2; (B) TOTAL NUMBER OF HYDRIDES I.E. THAT COMES FROM A AND FROM THE C4H9COO-H BOND DISSOCIATION. ..................................................................................................................................................... TABLE 3.8 DFT TITRATION COMPARISON BETWEEN RUX(CH3COOH)0.4 AND RUX(C4H9COOH)0.3 NPS. ........................................................................................................

TABLE 3 .

 3 9 H2 DISSOCIATIVE ADSORPTION GIBBS FREE ENERGY (ΔGH) COMPARISON IN DIFFERENT RU55 NP SITES BETWEEN RU55(CH3COO)16(H)16 AND RU55(C4H9COO)14(H)14 MODELS.

..................................................................................................................................................................................................................................

TABLE 3 .

 3 10 COMPARISON OF THE MEAN SIZES OF RUNPS (OBTAINED BY TEM) STABILIZED WITH THE SAME AMOUNT OF ETHANOIC, PENTANOIC AND OCTANOIC ACID. SOLVENT (A) PENTANE;

(B) THF. ......................................................................................................................................................................................................................

TABLE 3 .

 3 11 MEAN ADSORPTION ENERGIES CALCULATED FOR DIFFERENT CARBOXYLIC MOIETIES DEPOSED ONTO RU55 NP MODELS AT DIFFERENT COVERAGE VALUES. .............................

TABLE 3 .

 3 12 COMPARISON OF THE MEAN ADSORPTION ENERGY OF CARBOXYLIC MOIETIES IN A RU55(RCOO)14H144 NP OBTAINED BY DFT VS DFT-D3 METHODS. .........................

TABLE 3 .

 3 13 COMPARATIVE DATA IN TERMS OF REQUIRED QUANTITY OF CARBOXYLIC LIGAND TO STABILIZE RUNPS WITH SIMILAR MEAN SIZE. ...........................................................

TABLE 3 .

 3 14 COMPARISON OF THE CHEMICAL SHIFT OF FREE CARBOXYLIC ACIDS AND COORDINATED CARBOXYLATE DEPENDING ON THE ALKYL CHAIN LENGTH OF THE LIGAND USED FOR STABILIZE SOLID STATE; (C) CDCL3. ................................................................................................................................................................

	RUNPS. (A) THF-D

8

; (B)

TABLE 3 .

 3 15 QUANTIFICATION OF THE DIFFERENT TYPE OF INTERACTING LIGANDS SURROUNDING THE RUX(C7H15COOH)0.20 NPS. ........................................................................

TABLE 3 .

 3 16 DETERMINATION OF THE NUMBER OF LIGANDS PER RUNP AND OF THE RATIO OF RU SURFACE ATOMS PER LIGAND FOR EACH TYPE OF OCTANOIC LIGANDS SURROUNDING THE

RUX(C7H15COOH)0.20 NPS .............................................................................................................................................................................................. TABLE 3.17 C, H, N ANALYSIS OF RUX(C7H15COOH)0.20 NPS. ............................................................................................................................................................. TABLE 3.18 ICP-AES ANALYSIS OF RUX(C7H15COOH)0.20 NPS. ...........................................................................................................................................................

TABLE 3 .

 3 19 OPTIMIZED STRUCTURES USED FOR THE RUX(C7H15COOH)0.20 DFT SURFACE TITRATION. THE TOTAL NUMBER AND COVERAGE RATIO OF COORDINATED LIGANDS AND ITS CORRESPONDING DFT ENERGY (EV) ARE ALSO PROVIDED. (A) NUMBER OF HYDRIDES COMING FROM THE DISSOCIATIVE ADSORPTION OF H2; (B) TOTAL NUMBER OF HYDRIDES COMING FROM A AND FROM THE C7H15COO-H BOND DISSOCIATION. ....................................................................................................................................................

TABLE 3 .

 3 20 COMPARISON BETWEEN THE EXPERIMENTAL AND THEORETICAL SURFACE COVERAGE CHARACTERIZATION OF RUX(C7H15COOH)0.20 NPS. ...............................................

TABLE 3 .

 3 21 COMPARISON BETWEEN EXPERIMENTAL AND THEORETICAL TITRATIONS OF RUNPS STABILIZED BY THE STUDIED CARBOXYLIC ACID. .........................................................

TABLE 3 .

 3 22 ESTIMATED QUANTITIES OF THE DIFFERENT TYPE OF INTERACTING LIGANDS IN THE RUX(C7H15COOH)0.20 NPS DETERMINED BY DOSY NMR DATA. .................................

TABLE 3 .

 3 23 HYDRODYNAMIC DIAMETERS VS THE EXTRA-LIGAND ADDED FOR PREFORMED RUX(C7H15COOH)0.20 NPS. ......................................................................................

TABLE 3 .

 3 24 H2 DISSOCIATIVE ADSORPTION GIBBS FREE ENERGY (ΔGH). COMPARISON BY DIFFERENT RU55 NP SITES OF RU55(CH3COO)16(H)16, RU55(C4H9COO)14(H)14 AND RU55(C7H15COO)14(H)14 MODELS. ...................................................................................................................................................................................

TABLE 4 .

 4 1 DIFFUSION COEFFICIENTS OF OCTANOIC ACID AND BENZOIC ACID MOIETIES AND CORRESPONDING SIGNAL WEIGHT FOR EACH ADDITION OF BENZOIC ACID TO COLLOIDAL SUSPENSION OF RUX(C7H15COOH)0.20 NPS..........................................................................................................................................................................................

TABLE 4 .

 4 2 MAPPING OF THE RUNPS SURFACE AFTER LIGAND EXCHANGE EXPERIMENTS BETWEEN OCTANOIC AND BENZOIC ACID. ..........................................................................

TABLE 4 .

 4 3 DFT ENERGIES OBTAINED FOR LIGAND EXCHANGE REACTIONS BETWEEN OCTANOIC AND BENZOIC ACID ONTO RU55 NP. ........................................................................

TABLE 4 .

 4 4 AVERAGE ADSORPTION ENERGY IN RU55 NP COVERED BY OCTANOATES AND A MIXTURE OF CAPPED LIGANDS. .....................................................................................

TABLE 4 .

 4 5 DIFFUSION COEFFICIENTS OF OCTANOIC ACID MOIETIES AND CORRESPONDING SIGNAL WEIGHT FOR THE ADDITION OF TFA TO A COLLOIDAL SUSPENSION OF RUX(C7H15COOH)0.20 +

0.20 NPS. ......................................................................................................................................................................................................................

TABLE 4 .

 4 6 DOSY NMR DATA EXTRACTION OF THE QUANTITY OF DIFFERENT TYPE OF INTERACTING LIGANDS IN THE RUX(C7H15COOH)0.20 +0.20 NPS. ...............................................

TABLE 4 .

 4 7 COMPARISON OF THE LIGAND EXCHANGE REACTION DEPENDING ON THE NATURE OF THE INCOMING LIGAND, NAMELY BENZOIC ACID OR TRIFLUOROACETIC ACID.

TABLE A .

 A 1 HYDROGEN COVERAGE RATIO, HYDROGEN COORDINATION MODES, DFT ENERGY OF THE OPTIMIZED STRUCTURES AND HYDROGEN MEAN ADSORPTION ENERGY. .................... TABLE A.2 RU55 NP ADSORPTION SITE OF ETHANOIC ACID, CH3COOH COORDINATION MODE, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND ETHANOIC ACID ADSORPTION ENERGY.....

TABLE A .

 A 3 RU55 NP ADSORPTION SITE OF ETHANOATE, (CH3COO) COORDINATION MODE, DFT ENERGY OF THE OPTIMIZED STRUCTURE AND ETHANOATE ADSORPTION ENERGY. ............

TABLE A .

 A

TABLE E .

 E 1 ETHANOATE & HYDROGEN COVERAGE RATIOS, H COORDINATION SITE IN Μ MODE, HYDROGEN ADSORPTION ENERGY AND HYDROGEN GIBBS FREE ENERGY. ........................... TABLE E.2 PENTANOATE & HYDROGEN COVERAGE RATIOS, H COORDINATION SITE IN Μ MODE, HYDROGEN ADSORPTION ENERGY AND HYDROGEN GIBBS FREE ENERGY. ......................... TABLE E.3 OCTANOATE & HYDROGEN COVERAGE RATIOS, H COORDINATION SITE IN Μ MODE, HYDROGEN ADSORPTION ENERGY AND HYDROGEN GIBBS FREE ENERGY. ...........................

Table 1 .

 1 1 Close-packed magic number clusters. The rest of the metal surface atoms highlighted in blue are located in the NP faces.

				Number of shells
		1	2	3	4
	General
	description
	Size of RuNP (nm)	0.7	1.1	1.6	2.0
	Total number of metal atoms	13	55	147	309
	Number of
	surface atoms	92	76	63	52
	(%)
	Edge atoms (%)	0	54	41	29
	Corner atoms (%)	92	22	8	2

Table 1 .

 1 2 Experimental and theoretical techniques for determining RuNPs properties.

	CHAPTER I

table a comparison of the different analytical techniques, experimental and theoretical, to determine the RuNPs properties is presented (table 1.2).

Table 2 .

 2 2 EDX analysis for element quantification of oxygen & ruthenium ratio in comparison with the experimental synthesis relation for Ru x (CH 3 COOH) 0.2 NPs.

		Experimental relation	001 spot	002 spot
	[O]/[Ru] ratio	0.40	0.22	2.22

Table 2

 2

	.3 EDX analysis for element quantification of oxygen & ruthenium ratio ratio in comparison with the experimental
	synthesis relation for Ru x (CH 3 COOH) 0.4 NPs.
	Experimental relation	004 spot	005 spot
	[O]/[Ru] ratio	0.80	-----	0.47

  THF) at ca. 3.6 & 1.7 ppm, and a signal attributed to an oxidative impurity, water, at ca. 2.5 ppm. It is worthy to notice that no sharp signals at ca. 1.93 and 10.59 ppm can be observed as expected for the methyl (-CH 3

	1 H-NMR) spectrum was recorded from the
	Ru x (CH 3 COOH) 0.4 NPs (figure 2.15) after several washings with pentane-THF cycles and drying
	under high-vacuum during half a day. For achieving the NMR measurements, the nanoparticles
	were re-dispersed in THF-d 8 .
	The RuNPs experimental 1 H-NMR spectrum (figure 2.15 blue) was compared with that of
	the pure ethanoic acid (figure 2.15 red). It is important to note that this later corresponds to the
	carboxylic acid dimer and not to the isolated molecule. The 1 H-NMR spectrum of the nanoparticles
	shows signals of the NMR solvent (

  ppm in THF-d[START_REF] Liu | Pd nanoparticle assemblies as efficient catalysts for the hydrogen evolution and oxygen reduction reactions[END_REF] ). Owing to these results it can be said that no free carboxylic species are present in the deuterated solution and that the broad signal at ca. 2.08 ppm found in the experimental spectrum does not correspond to any of

	According to the DFT chemical shift results obtained in the [Ru 6 ] nanocluster, there is no
	doubt that the signal experimentally observed at ca. 2.14 ppm cannot be assigned to free
	carboxylic moieties nor to ethanoic acid coordinated onto the NPs surface but to chemisorbed
	ethanoate and probably in a bidentate coordination mode.
	Figure 2.18 DFT mean methyl protons chemical shift of CH 3 COOH interacting with [Ru 6 ] nanocluster in different
	coordination modes; (a) η; (b) μ.
	the ethanoic acid or ethanoate free entities
	Thus, calculations of chemical shifts of methyl protons of ethanoic acid or ethanoate
	species when interacting with the Ru 6 nanocluster were performed. First it was observed, that the
	methyl protons are always unshielded compared with the free ethanoic acid dimer. The chemical
	shift observed for moieties interacting as carboxylic acid were found to be ca. [2.6 -2.9 ppm]
	depending on the coordination mode (figure 2.18). These values mean that the direct ligand
	interaction with the nanocluster leads to deshielded signals at least by ca. 0.7 ppm. These values
	are different from the signal at 2.08 ppm observed on the experimental 1 H NMR spectrum, thus
	indicating that the ethanoic acid ligand is probably not coordinated as a carboxylic acid.
	Roberto González Gómez Roberto González Gómez	82 83

Similar calculations were then done by focusing on the ethanoate interaction mode. For this case, three different coordination modes were analyzed: chair, monodentate and bidentate (figure

2

.

19

). The results show also a proton deshielding in comparison with the free ligand moieties, but not as high as that found for the ethanoic acid moiety. In fact, the chemical shift of the ethanoate methyl protons coordinated in a bidentate mode (ca. [2.0 -2.2 ppm]) is in the range of the broad signal observed in the experimental spectrum. The other two coordination modes are at higher ppm values (chair ca. 2.6 ppm; monodentate ca. 2.3 ppm) and do not correspond to the experimental data.

Figure 2.19 DFT mean methyl protons chemical shift of CH 3 COO moiety interacting with [Ru 6 ] nanocluster in different coordination modes; (a) chair: σ carbon, μ

  Tanner equation. The decay could not be fitted with a mono-exponential model and only a bi-exponential analysis least-square fitting leads to a perfectly match of the experimental data.

	This diffusional attenuation is shown in figure 2.23 and it was fitted with the classical
	Stejskal-
		3 COOH) 0.4 NPs
	(figure 2.23) evidenced signals of species with fast mobility (high diffusion coefficient) that were
	attributed to water and THF due to their chemical shift.
	The 2D-DOSY NMR experiment for Ru x (CH 3 COOH) 0.4 NPs (figure 2.23) evidenced signals of
	moieties with fast mobility (high diffusion coefficient) that were attributed to water and THF.
	However, there is another organic moiety which is heavier and diffuse slower in the deuterate
	solvent, as it was observed in the diffusion-filtered DOSY 1 H-NMR. The overlapping of the broad
	signal and solvents make the DOSY data difficult to analyze. Nevertheless, interesting results could
	be obtained by following the evolution of the integration of the [1.9 -2.2 ppm] area, that contains
	mostly signals of methyl groups of strongly or weakly bonded ethanoic acid molecules, with the
	gradient strength.
	Roberto González Gómez	87

  Ru surf atoms) the ethanoates surface coverage should be ca. 15 CH 3 COO(H)/Ru NP . The hydride surface composition in model 2 is slightly beyond the experimental evidence (see section 2.5.1).

	.24 a; 1) was based on a bare Ru 55 NP, thus the calculated
	energy profile derives from the direct interaction of the carboxylic moiety and the initial Ru 55 NP
	model. The second analyzed model (figure 2.24 b; 2) was created from the same base model (Ru 55
	NP) but considering some experimental findings. 1 H-NMR provides some insights of the
	carboxylate presence, in addition of the reductive media (H 2 ) used for the RuNPs synthesis. Hence,
	the model was decorated with 15 ethanoates and 32 hydrides. In this last model (2), the
	ruthenium surface accommodates 0.4 carboxylates and 0.7 hydrides per ruthenium surface atom
	(CH 3 COO/Ru surf & H/Ru surf ). Among the 32 hydrides, 15 derive from the carboxylic acid
	deprotonation meanwhile the rest comes from the reductive media.
	The surface composition is close to that determined experimentally by DOSY NMR
	experiments (28 CH 3 COO(H)/Ru NP ). Indeed, considering that in ca 1.5 nm NPs, the number of
	ruthenium surface atoms is ca. 83 Ru surf atoms. It can be inferred that for a 1.0 nm Ru 55 NP (44
	Roberto González Gómez	91

  , thus reduces the Ru 55 NP d-band center energy and therefore weakens the adsorption strength of the ethanoic acid on the ruthenium metal surface (see section 2.6.1).([172],[START_REF] Mott | Synergistic activity of gold-platinum alloy nanoparticle catalysts[END_REF])

	the antibonding states
		1 , (figure 2.25; 2 -CH 3 COOH*; red profile). This value is
	in the same range to the dissociative adsorption energy of H 2 on bare Ru 55 NP surface and close to
	that on crowded hydrogenated Ru 55 NP, 2H* ca. -28.8 & -24.0 kcal.mol -1 , respectively (see section
	appendix A.1).
	Although no steric hindrance impedes the grafting of an ethanoic acid in the model 2, the
	presence of hydrides and ethanoates in the vicinity of the grafting site, increases the fullness of
	Roberto González Gómez	92

  obtained as free ligands and as coordinated species onto a [Ru 6 ] nanocluster (scheme 2.6) by following the previously decribed methodology (see section 2.3.1).

	Scheme 2.6 [Ru 6 ] nanocluster geometrical illustration.

C-NMR signal was corroborated by DFT calculations followed by elucidation of the probable ligand molecular structure. In these calculations, the carbon chemical shifts of protonated-unprotonated carboxylic Roberto González Gómez 96 acid were

Table 2 .

 2 4 Optimized structures used for the DFT surface titration. The total number and coverage ratio of coordinated ligands are also shown with the corresponding DFT energy (eV). (a) Number of hydrides that come from the dissociative adsorption of H 2 ; (b) total number of hydrides i.e. that comes from a and from the CH 3 COO-H bond dissociation.

8 of them (figure 2.36) appear to be stable in the considered pressure and concentration domains. It can be seen that at high hydrogen pressure and low ethanoic acid concentration, the most stable Ru 55 NP structures are the one covered with

  Figure 2.36 Most stable [Ru 55 ] structures in each domain. (Domain 39: Ru 55 (CH 3 COO) 16 (H) 16 ; domain 40: Ru 55 (CH 3 COO) 16 (H) 25 ; domain 19: Ru 55 (CH 3 COO) 4 (H) 74 ; domain 37: Ru 55 (CH 3 COO) 14 (H) 14 ; domain 3: Ru 55 (H) 35 ; domain 7: Ru 55 (CH 3 COO)(H) 54 ; domain 8: Ru 55 (CH 3 COO)(H) 71 ; domain 5: Ru 55 (H) 70 ).

	almost only hydrides (domain 3 & 5) or a low quantity of them (domain 7).
	Roberto González Gómez	111

  CH 3 COO/Ru surf lie on the

	RuNP surface. This ratio suggests that around 15 carboxylates are expected to be strongly bonded
	onto the Ru 55 NP model, in very reasonable agreement with the surface composition found for
	domains 39 and 40. Both theoretical studies and experimental findings are thus in a good
	agreement about the RuNPs surface composition. It further validates the theoretical approach and
	it provides an accurate mapping of the surface-capping ligands presented in the surface of the
	Ru x (CH 3 COOH) 0.4 NPs.
	The surface coverage was also evaluated at low temperature (200 K) in order to evaluate
	what the surface composition would be if a hypothetical synthesis could be performed at this
	temperature (figure 2.37).
	Roberto González Gómez	113

stable at 200 K (figure 2.37). In comparison with the phase diagram presented at 300 K (figure

  Figure 2.38 Additional stable [Ru 55 ] clusters found at 200 K. (Domain 41: Ru 55 (CH 3 COO) 16 (H) 33 ; domain 35: Ru 55 (CH 3 COO) 12 (H) 65 ).

	2.36) two new optimized structures (figure 2.38) can be observed at low concentration-pressure of
	both ligands (domain 35; Ru 55 (CH 3 COO) 12 (H) 65 ) and the other one at high concentration-pressure
	(very small domain 41; Ru 55 (CH 3 COO) 16 (H) 33 ).
	Roberto González Gómez	114

  Figure 2.40 Additional stable [Ru 55 ] clusters found at 450 K. (Domain 27: Ru 55 (CH 3 COO) 10 (H) 10 ; domain 1: Ru 55 ; domain 2: Ru 55 (H) 17 ; domain 3: Ru 55 (H) 53 ). Now, domains 39 and 40, found to be the more stable at 200 and 300K, can be found by significantly increasing 𝑝 𝐻 2 and [CH 3 COOH]. If we focus on the same pressure and concentration

	similar adsorption energies, steric hindrance, pressure & concentration and temperature could
	explain this drastic change in the surface composition on going from domain 37 to domain 7.
	ramges as done for the other temperatures (𝑝 𝐻 2 : [10 -5 -10 0 bar]; [CH 3 COOH]: [10 -4 -10 -1 mol.L -1 ]), a
	new domain (37) dominates and less probably a completely different domain (7).
	The temperature increase involves to significantly decreasing the amount of carboxylic
	acid and hydrogen in the surrounding medium, this phenomenon can be observed for the domain
	37 where the Ru 55 NP can accommodate 14 CH 3 COO/Ru surf and the same amount of hydrides
	coming from the carboxylic acid deprotonation 14 H/Ru surf . Although the dissociative adsorption
	energy of H 2 is low compared to CH 3 COOH, when 𝑝 𝐻 2 is high enough, there is a competition
	between hydrides and ethanoates. This is what is observed in domain 7, with a remarkable
	reversal of the H/ethanoate stoichiometry (1 CH 3 COO/Ru surf and 54 H/Ru surf ) for a low acid
	concentration and a significantly high pressure of hydrogen.
	.39) new stable optimized This can be explained in terms of the metal surface energy, which relies upon the
	structures can be found at certain 𝑝 𝐻 2 and [CH 3 COOH] ranges. These structures (figure 2.40) are adsorption strength of each ligand and on the total number of ligands that are bound on a given
	stabilized by less quantity of ligands (domain 27), or even only by hydrides (domains 2 & 3). If the metal surface area (see section 6.2.6). It turns out that on a crowded metal surface the dissociative
	pressure and concentration conditions are too low, the surface of the Ru 55 NP cannot be stabilized adsorption strength of an ethanoic acid is ca. -26.7 kcal.mol -1 (CH 3 COO: 16; H: 51; see section
	(domain 1). In this case, such NPs would probably not exist, since such 1.0 nm NP would probably appendix A.4) i.e. it is not significantly higher than the dissociative adsorption energy of H 2 (ca. -
	coalesce to form larger systems. Again, the coordinates of these structures can be found in section 24.0 kcal.mol -1 ; H: 70; see section appendix A.1). Yet, owing to steric hindrance considerations, a
	appendix F. given surface area cannot accommodate as many ethanoates as hydrides. The balance between
	Roberto González Gómez Roberto González Gómez	116 117

  𝑅𝑢 𝑠 : 0.19e). Meanwhile, the dissociative grafting of 16 ethanoic acids Ru 55 (CH 3 COO) 16 (H) 33 involves a stronger oxidation of the ruthenium surface atoms (𝑞 𝑅𝑢 𝑠 : 0.35e). Ru metal atoms on which carboxylates are grafted are even more oxidized, with charges that reach ca. 0.5e.

).

Whereas in the Ru 55 (H) 17 , hydrides hold a negative charge (𝑞 𝐻𝑦𝑑𝑟𝑖𝑑𝑒 : -0.27e) thus involving a small Roberto González

Gómez 129

oxidation of these atoms (𝑞

  This induced a decrease in the hydrogen adsorption energy which explains the difference in the obtained hydrogen adsorption Gibbs free energy (ΔG H* ).Nevertheless, regarding the d-band center mapping, there is not a significant difference between the two crowded models, that show similar values for the surface atoms (𝜀̅ 𝑑,𝑠 = -2.90 eV). This result indicates that, the difference observed between the studied models cannot be explained by the d-band center model. Hence, the weaker H-adsorption calculated in Ru 55 (CH 3 COO) 16 (H) 16 could be attributed to a strong Coulomb repulsion between the adsorbed hydride and the surface ethanoates which can have an effect on the whole surface energy of the Ru 55 NP.

The overall calculated H 2 dissociative adsorption Gibbs free energies in the ethanoates saturated model, Ru 55 (CH 3 COO) 16 (H) 16 , are weaker than those calculated for the hydrogenated model Ru 55 (CH 3 COO)(H) 54 on the same representative sites (ca. -2.3 vs -4.5 kcal.mol -1 ). Also, it shows less influence for the adsorption site, except for the apex region (B 4 and B 5 site) all the other sites hold similar ΔG H* values. The difference between the two crowded Ru 55 NP models, Ru 55 (CH 3 COO) 16 (H) 16 and Ru 55 (CH 3 COO)(H) 54 , was previously noted in the overall calculated Gibbs free energies which were plotted in the phase diagram at 300 K. It was observed that the Ru 55 (CH 3 COO) 16 (H) 16 model was more stable given a decrease of the Ru 55 NP surface energy, which was attributed to the presence Roberto González Gómez 133 of adsorbed ethanoates. The low hydrogen adsorption energies found in Ru 55 (CH 3 COO) 16 (H) 16 , which is the most accurate model with respect to experimental data, locate this catalyst on top of the volcano plot

Table 3 .

 3 1 Sweep of pentanoic acid molar equivalents used for the synthesis of RuNPs. * Previously described.

		System	Pentanoic acid (equiv.)
	1	Ru x (C 4 H 9 COOH) 0.05	0.05
	2	Ru x (C 4 H 9 COOH) 0.2	0.20
	3	Ru x (C 4 H 9 COOH) 0.3	0.30
	4*	Ru x (C 4 H 9 COOH) 0.4	0.40
	5	Ru x (C 4 H 9 COOH) 0.5	0.50
	6	Ru x (C 4 H 9 COOH) 0.6	0.60

Table 3 .

 3 2 Scope of pentanoic acid quantity used for the RuNPs synthesis with their corresponding mean size and size dispersion obtained by TEM analyses.

		System	Pentanoic acid (equiv.)	Mean size (nm)	Size dispersion (2σ, nm)
	1	Ru x (C 4 H 9 COOH) 0.05	0.05	0.75 3.36	0.34 2.48
	2	Ru x (C 4 H 9 COOH) 0.20	0.20	1.58	0.47
	3	Ru x (C 4 H 9 COOH) 0.30	0.30	1.47	0.40
	4	Ru x (C 4 H 9 COOH) 0.40	0.40	1.13	0.31
	5	Ru x (C 4 H 9 COOH) 0.50	0.50	1.18	0.18
	6	Ru x (C 4 H 9 COOH) 0.60	0.60	1.02	0.26

Table 3 .

 3 3 Different groups found by sweeping the pentanoic acid concentration for the RuNPs synthesis.

	Group	Pentanoic acid (equiv.)	Mean size (nm)
	1	0.05	Mixture
	2	0.20 -0.30	1.5
	3	0.40 -0.60	1.1

  Hydrodynamic diameters measured by DOSY analyses exhibit the presence of small and ultra-small nanoparticles, which were difficult to observe by TEM analyses. Therefore, it can be estimated that the count performed by microscopy techniques was accurate enough to display the mean size of the synthetized RuNPs In addition, by these DOSY NMR analyses nano-objects smaller than ca. 1.1 nm are observed (≥ 0.40 equiv. of ligand added). Such small NPs are very difficult to observe by TEM analyses due to their small size and microscopy resolution. Nevertheless, the TEM histograms built for NPs systems prepared with [0.40 to 0.60 equiv.] of ligand report smaller NPs than 1.0 nm.

			Pentanoic acid	Diffusion coefficient	D H	RuNPs
			(equiv.)	(m	2 .s -1 )	(nm)	(nm)
	1	Ru x (C 4 H 9 COOH) 0.05	0.05	5.59x10 -10	1.69	0.49
	2	Ru x (C 4 H 9 COOH) 0.20	0.20	3.40x10 -10	2.77	1.57
	3	Ru x (C 4 H 9 COOH) 0.30	0.30	3.14x10 -10	3.00	1.80
	4	Ru x (C 4 H 9 COOH) 0.40	0.40	4.24x10 -10	2.22	1.02
	5	Ru x (C 4 H 9 COOH) 0.50	0.50	4.54x10 -10	2.08	0.88
	6	Ru x (C 4 H 9 COOH) 0.60	0.60	4.75x10 -10	1.99	0.79
	Roberto González Gómez					167

Also, DOSY analyses indicate an absence of size limit even at high concentration of pentanoic acid (0.60 equiv.) while a plateau at a mean size of ca. 1.1 nm was deduced from TEM results for RuNPs prepared with [0.40 -0.60 equiv.] of ligand. Implicating that the RuNPs mean size is inversely proportional to the amount of stabilizing agent added for the RuNPs synthesis.

Finally, it was noted from TEM studies that between [0.20 -0.30 equiv.] of pentanoic acid added to the reaction media, statistical similar size of RuNPs were produced. An analogous phenomenon was observed for NPs stabilized by ≥ 0.40 equiv. of pentanoic acid, which makes the assignation of RuNPs groups reliable. Table

3

.5 gives a comparison of the data obtained by TEM and DOSY NMR techniques. It appears that the two techniques provided complementary data, that for some of them are perfectly in agreement while others underestimated. Nevertheless, it can be concluded that the results obtained are reliable enough to provide a good idea of the influence of the quantity of pentanoic acid on the size of the RuNPs formed in a concentration rang of [0.05 to 0.60 equiv.].

Roberto González Gómez 168

Table 3 .

 3 5 Comparison between the data obtained by TEM studies vs DOSY analyses for RuNPs synthetized with different quantities of pentanoic acid. Solid-NMR Studies of Ru x (C 4 H 9 COOH) 0.3 NPs

		System	(equiv.) Pentanoic acid	(nm) Metal D H	(nm) TEM size	Group
	1	Ru x (C 4 H 9 COOH) 0.05	0.05	0.49	0.75 3.36	1
	2 3	Ru x (C 4 H 9 COOH) 0.20 Ru x (C 4 H 9 COOH) 0.30	0.20 0.30	1.57 1.80	1.58 1.47	2
	4	Ru x (C 4 H 9 COOH) 0.40	0.40	1.02	1.13
	5	Ru x (C 4 H 9 COOH) 0.50	0.50	0.88	1.18	3
	6	Ru x (C 4 H 9 COOH) 0.60	0.60	0.79	1.02
	3.1.7 Evaluation of Ru(C 4 H 9 COOH) 0.3 NPs

As mentioned before, the main objective of section 3.1.6 was to test different quantities of ligand in order to obtain pentanoic-acid stabilized RuNPs of ca. 1.5 nm in size as for Ru x (CH 3 COOH) 0.4 NPs. In order to reduce one of the variables (NPs size and alkyl chain length) presented for comparing the influence of the ligand (ethanoic acid vs pentanoic acid) in the RuNPs properties.

From the previous experiments, two [ligand]/[metal] ratio allowed to reach this aim, namely 0.2 and 0.3 equiv. The Ru x (C 4 H 9 COOH) 0.3 NPs was selected because it was observed by TEM analysis that the RuNPs presented a more homogenous population with similar mean size as Ru x (CH 3 COOH) 0.4 (see section 3.1.6). Despite the efforts made to decrease the variables, another parameter comes out, the probable quantity of capping ligand interacting with the NPs surface (0.3 vs 0.4 equiv.). obtain the chemical shift of the carboxylic species present in this NPs system (figure

3

.17), in comparison with previous findings observed (see section 2.4.2) and to elucidate if the ligand is coordinated as carboxylic acid or carboxylate.

Table 3 .

 3 6 Elemental analysis of Ru x (C 4 H 9 COOH) 0.3 NPs

	Element	Sample weight (%)
	C	22.4
	H	2.0
	N	0.1

  DFT-PBE together with the ab initio thermodynamics methodology (see section 6.2.6) can describe the structural, spectroscopic and electronic properties of RuNPs stabilized by carboxylic acids with high accuracy.

	CHAPTER III	Pentanoic Acid-Capped RuNPs
	actual case; (iii)
	capping ligands were experimentally quantified by DOSY NMR (0.3 CH 3 COO/Ru surf ) and norbornene
	reduction (0.3 H/Ru surf ). Also, a theoretical counterpart was performed by DFT titration, where two
	stable structures with (0.4 CH 3 COO/Ru surf ) and ([0.4 -0.6] H/Ru surf ) were found to be stable at r.t.,
	see domains 39 and 40 in figure 2.35 (their respective stability being related to the concentration
	of acid and pressure of H 2 ).
	Roberto González Gómez	172

3.1.7.3 Theoretical Titration of Ru x (C 4 H 9 COOH) 0.3 NPs

In chapter II, a combination of theoretical and experimental characterizations proved that hydrides and deprotonated ethanoic acids interact with the Ru x (CH 3 COOH) 0.4 NPs surface. These On the basis of the ethanoic acid case described in the previous chapter, it can be inferred that (i) theoretical and experimental findings have a high degree of agreement regarding the surface properties of ruthenium NPs; (ii) the theoretical Ru 55 NP model (see section 6.2.1), although slightly smaller than the actual experimental NPs, allows a relevant extrapolation to the

Table 3 .

 3 7 Optimized structures used for the Ru x (C 4 H 9 COOH) 0.3 DFT surface titration. The total number and coverage ratio of coordinated ligands are also given with its corresponding DFT energy (eV). (a) Number of hydrides that come from the dissociative adsorption of H 2 ; (b) total number of hydrides i.e. that comes from a and from the C 4 H 9 COO-H bond dissociation.

  3 C 4 H 9 COO/Ru surf . This data can be extrapolated to the experimental hcp 1.47 nm RuNPs (mean size obtained by TEM), which has an estimated of 79 ruthenium surface atoms that represents the 65.0 % of the total metal atoms of the NP. As a result, the RuNPs can accommodate around 25 pentanoates directly interacting with the Ru x (C 4 H 9 COOH) 0.3 NPs surface. The same ligand vs ruthenium surface atoms ratio was found for hydrides (0.3 H/Ru surf ).

These results can be compared (table

3

.8) with those obtained for Ru x (CH 3 COOH) 0.4 NPs that displays similar mean size of the metal core. The amount of ethanoates required to stabilize the RuNPs was 0.4 CH 3 COO/Ru surf and the quantity of hydrides was [0.4 -0.6] H/Ru surf . These data CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 177

  .8 DFT titration comparison between Ru x (CH 3 COOH) 0.4 and Ru x (C 4 H 9 COOH) 0.3 NPs. These theoretical results are in line with experiments, since Ru x (C 4 H 9 COOH) 0.3 NPs were stabilized with 0.1 equiv. less ligand than the Ru x (CH 3 COOH) 0.4 NPs. Both investigations agree to

		Carboxylate	Hydrides
	NP system
		(RCOO/Ru surf )	(H/Ru surf )
	Ru x (CH 3 COOH) 0.4	0.4	[0.4 -0.6]
	Ru x (C 4 H 9 COOH) 0.3	0.3	0.3

  -1 to ΔE H ; see section 6.2.11). A good catalyst must possess sites for which ΔG H is close to zero. Owing to the good agreement previously obtained between experimental and computational chemistry characterization (see chapter II), the catalytic performance of Ru x (C 4 H 9 COOH) 0.3 NPs can be assessed for HER reaction by looking at the hydrogen adsorption energy (ΔE H ) on the most stable Ru 55 NP structure found by DFT titration, namely Ru 55 (C 4 H 9 COO) 14 (H) 14 .

To fulfill this procedure, the hydrogen adsorption energy (ΔE H ) was obtained in five different selected sites on the Ru 55 (C 4 H 9 COO) 14 (H) 14 NP, i.e. planes (001) and (

101

) and the enclosing B 4 & B 5 zone of the Ru 55 NP model (see section 6.2.1), which involve different type of interactions. The corresponding ΔG H values (see section appendix E.2) are reported in the figure 3.21. CHAPTER III Pentanoic Acid-Capped RuNPs Roberto González Gómez 179

Table 3 .

 3 9 H 2 dissociative adsorption Gibbs free energy (ΔG H ) comparison in different Ru 55 NP sites between Ru 55 (CH 3 COO) 16 (H) 16 and Ru 55 (C 4 H 9 COO) 14 (H) 14 models.

	Site	Ru 55 (

CH 3 COO) 16 (H) 16 Ru 55 (C 4 H 9 COO) 14 (H) 14

	(001)	-2.5	-4.8 & -0.6
	(101)	-2.3, -1.9 & 2.4	-7.8 & -4.8
	B 4 &B 5	-7.9	0.8

  to form Ru x (C 7 H 15 COOH) 0.4 ) THF NPs, a ruthenium organometallic precursor Ru x (C 7 H 15 COOH) 0.4 ) THF NPs appeared highly stable without any precipitate formed after one week.

	CHAPTER III	Octanoic Acid-Capped RuNPs
	colloidal solution of (
	([Ru(COD)(COT]) dissolved in THF (2 mL of THF/3 mg of [Ru]).and in the presence of 0.4 equiv. of
	octanoic acid (stabilizing agent), was decomposed under reductive atmosphere (3 bar H 2 ) at r.t.
	inside a Fisher-Porter reactor under vigorous stirring, as it was described in section 6.1.2.2. When
	exposed to hydrogen, the yellow solution turned brownish after ca. 60 s and then changed to
	black within another ca. 30 s. The reactor was left under dynamic hydrogen pressure for 30
	Roberto González Gómez	185

minutes and then under static pressure for 15 h. The reaction was stopped by evacuation of the remaining hydrogen atmosphere under high-vacuum and its replacement by argon. The obtained

table 3

 3 the NP size did not decrease compared to that of Ru x (C 4 H 9 COOH) 0.4 . This effect can be attributed to the use of THF instead of pentane, vide infra. However, it appeared that the (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs display a more homogeneous shape than the Ru x (C 4 H 9 COOH) 0.4 NPs. In

	CHAPTER III

.10, the (Ru x (C 7 H 15 COOH) 0.4 ) THF NPs have a mean size intermediate to that of Ru NPs prepared with ethanoic acid and pentanoic acid at the same [ligand]/[ruthenium]

ratio. Thus, despite the increase of the alkyl chain length when passing from pentanoic to

Table 3 .

 3 10 Comparison of the mean sizes of RuNPs (obtained by TEM) stabilized with the same amount of ethanoic, pentanoic and octanoic acid. Solvent (a) pentane; (b) THF.

	Nanosystem	Mean size (nm)	Distribution (2σ; nm)
	Ru x (CH 3 COOH) 0.4 a	1.51	0.58
	Ru x (C 4 H 9 COOH) 0.4 a	1.13	0.31
	Ru x (C 7 H 15 COOH) 0.4 b	1.34	0.51

Table 3 .

 3 11 Mean adsorption energies calculated for different carboxylic moieties deposed onto Ru 55 NP models at different coverage values.

	Nanosystem	Ethanoic acid (E ads ; kcal.mol -1 )	Pentanoic acid (E ads ; kcal.mol -1 )	Octanoic acid (E ads ; kcal.mol -1 )
	Ru 55 (RCOO) 10 H 10	-52.3	-46.3	-45.8
	Ru 55 (RCOO) 12 H 12	-51.7	-46.2	-43.8
	Ru 55 (RCOO) 14 H 14	-51.9	-45.4	-44.7

Table 3 .

 3 12 Comparison of the Mean adsorption energy of carboxylic moieties in a Ru55(RCOO)14H144 NP obtained by DFT vs DFT-D3 methods.

	Ru 55 NP	DFT-D3 energy	E ads -DFT-D3	E ads -DFT
	system	(eV)	(kcal.mol	-1 )	(kcal.mol -1 )
	Ru 55 (CH 3 COO) 14 H 14	-1128.71	-59.2		-51.9
	Ru 55 (C 4 H 9 COO) 14 H 14	-1825.27	-53.9		-45.4
	Ru 55 (C 7 H 15 COO) 14 H 14	-2522.70	-52.9		-44.7

  The size histogram built for (Ru x (C 7 H 15 COOH) 0.15 ) THF NPs gives a mean size of ca. 1.51 ± 0.80 nm (figure 3.28 b) and that of the (Ru x (C 7 H 15 COOH) 0.30 )

THF NPs a mean size of ca. 1.49 ± 0.71 nm (figure 3.29 d).

  Ru x (C 7 H 15 COOH) 0.4 ) THF NPs for comparison purpose.In the [1750 -1600 cm-1 ] area (green zone) where are expected the vibration bands of octanoic acid in its protonated form (either free or coordinated), the system (Ru x (C 7 H 15 COOH) 0.15 ) THF NPs does not show any vibrational bands meaning the absence of free and of protonated coordinated ligand (figure 3.30 a), which suggest that all the introduced ligand is coordinated under the form of octanoate. For the two other systems some signals are visible. While (Ru x (C 7 H 15 COOH) 0.40 ) THF NPs present two signals attributed to free and coordinated octanoic ligand, the (Ru x (C 7 H 15 COOH) 0.30 ) THF NPs show only one band, that is attributed to coordinated octanoic acid.

	CHAPTER III				Octanoic Acid-Capped RuNPs
		𝑠 1 ) 2 (𝑠 2 ) 2	𝐹 (500,500)𝛼=0.01 = 1.23
		𝐻0: 𝑆 1 = 𝑆 2	𝐻1: 𝑆 1 ≠ 𝑆 2
		𝐹 =	(0.35) 2 (0.25) 2 = 1.93	∴ 𝐻0 𝑖𝑠 𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑
		𝑡 =	𝑋 1 ̅̅̅̅ -𝑋 2 ̅̅̅̅ √ 𝑠 1 2 𝑛 1 𝑛 2 + 𝑠 2 2	𝑡 (∞)𝛼=0.01 = 2.57
		𝐻0: 𝑋 1 ̅̅̅ = 𝑋 2 ̅̅̅	𝐻1: 𝑋 1 ̅̅̅ ≠ 𝑋 2 ̅̅̅
	𝑡 =	1.49-1.34 √ (0.35) 2 400 400 + (0.25) 2	= 6.86	∴ 𝐻0 𝑖𝑠 𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑
	In the region of the CO stretching vibration [2100 -1800 cm -1 ] all the three nanosystems
	show vibration bands corresponding to terminal CO resulting from THF degradation (zone
	highlighted in blue), but the bands are more intense for the systems stabilized by 0.30 and 0.40
	equiv. of octanoic acid (figure 3.29 b and c respectively), showing different types of CO
	Roberto González Gómez				200

According to the statistical tests performed on the populations of (Ru x (C 7 H 15 COOH) 0.30 ) THF and (Ru x (C 7 H 15 COOH) 0.40 ) THF NPs, it can be concluded that there is a significant difference with 99.0% of level of reliability between these two systems of RuNPs. It appeared that a ligand quantity over to 0.30 equiv. has a direct influence on the mean size of the RuNPs, but no when lesser quantity is added (0.30 vs 0.15 equiv.).

Since the RuNPs stabilized with 0.40 equiv. of octanoic acid showed the presence of ligand excess, the nanosystems stabilized with 0.30 and 0.15 of ligand equiv. will be analyzed by infrared in similar conditions (see section 6.1.3.3) from purified NPs. The FTIR data are provided on figure

3

.29. together with those of (coordination modes or sites. Thus, evidencing a lower coordination/reactivity of THF at the NP surface prepared in the presence of 0.15 equiv. ligand.

  see the real advantage to use octanoic acid as stabilizing agent by removing the coordinated solvent variable (THF). The synthetic procedure was performed as described in section 6.1.2.2. The reactants ([Ru(COD)(COT)] & octanoic acid) were dissolved in n-pentane inside a Fisher-Porter reactor. Then the reaction mixture was exposed to 3 bar of H 2 under vigorous stirring. The initial yellowish solution turned black in ca. 15 s and metal pieces have fallen down at the bottom of the reactor in less than 30 s.

	CHAPTER III	Octanoic Acid-Capped RuNPs
	was chosen to
	Roberto González Gómez	203

10 equiv. of octanoic acid in a pentane solution (Ru x (C 7 H 15 COOH) 0.10 ). This quantity

  acids that have longer alkyl chain length (Ru x (C 7 H 15 COOH) 0.20 ) vs shorter ones (Ru x (C 4 H 9 COOH) 0.30 & Ru x (CH 3 COOH) 0.40 ).

	CHAPTER III	Octanoic Acid-Capped RuNPs
	stabilized with carboxylic
	Roberto González Gómez	206

Table 3 .

 3 13 Comparative data in terms of required quantity of carboxylic ligand to stabilize RuNPs with similar mean size. Structural Analysis of Ru x (C 7 H 15 COOH) 0.20 NPs Structural analysis of Ru x (C 7 H 15 COOH) 0.20 NPs was firstly performed by HRTEM using, the same grid as for TEM analysis. The HRTEM images revealed well-crystalline RuNPs displaying numerous atomic plans that lead to determine easily their crystalline structure (figure3.32 a). FFT Compared to those RuNPs prepared with 0.4 equiv. of ethanoic acid (Ru x (CH 3 COOH) 0.40 NPs) which were poorly crystallized, Ru x (C 7 H 15 COOH) 0.20 NPs present a high crystalline character and there is no doubt about the atomic packing.

	Nanosystem	Quantity of ligand (equiv.)	Mean size (nm)	Size dispersion (nm)
	Ru x (CH 3 COOH) 0.40	0.40	1.51	0.60
	Ru x (C 4 H 9 COOH) 0.30	0.30	1.47	0.40
	Ru x (C 7 H 15 COOH) 0.20	0.20	1.65	0.65
	In the following sections, the structural analysis and composition analysis of the
	Ru x (C 7 H 15 COOH) 0.20 NPs will be described
	3.2.5.1 of the HRTEM images allowed to measure interplanar distances of 0.214, 0.207, 0.134 and 0.112
	that could be attributed to crystalline (002), (101), (110) and (201) plans of the bulk ruthenium
	hexagonal close pack structure (figure 3.33 b)

  Ru x (C 7 H 15 COOH) 0.20 NPs.3.2.5.2 Organic Molecules Surrounding the Ru x (C 7 H 15 COOH) 0.20 NPs SurfaceFTIR study was performed with the aim to see which products can be found surrounding the formed nanoparticles, especially to discover if the octanoic acid act as protonated or deprotonated entity when is used as RuNPs stabilizer. The vibrational spectroscopy analysis of Ru x (C 7 H 15 COOH) 0.20 NPs was performed in the solid-state under inert atmosphere in a glove-box after dispersing the material into dried KBr. (see section 6.1.3.3).

	CHAPTER III	Octanoic Acid-Capped RuNPs
	Roberto González Gómez	209

After their structural analysis by HRTEM and WAXS, the composition of the particles was determined by FTIR and NMR experiments.

Table 3 .

 3 14 Comparison of the chemical shift of free carboxylic acids and coordinated carboxylate depending on the alkyl chain length of the ligand used for stabilize RuNPs. (a) THF-d

			Chemical shift observed for	Chemical shift of the free
	Nanosystem	Stabilizing agent	coordinated carboxylates	ligands
			(ppm)	(ppm)
	Ru x (CH 3 COOH) 0.40	Ethanoic acid	186.0	171.7	a
	Ru x (C 4 H 9 COOH) 0.30	Pentanoic acid	187.9	174.0	b
	Ru x (C 7 H 15 COOH) 0.20	Octanoic acid	192.1	180.4	c

8 ; (b) Solid state; (c) CDCl 3 .

Table 3 .

 3 15 Quantification of the different type of interacting ligands surrounding the Ru x (C 7 H 15 COOH) 0.20 NPs. the number of ligands per RuNP and also the ratio of surface Ru atoms per ligand (table 3.16), providing thus an approximative mapping of the surface of the Ru x (C 7 H 15 COOH) 0.20 NPs.

	Type of interaction Diffusion coefficient	Signal weight	Quantity of ligand
		(m	2 .s -1 )	(%)	(equiv.)
	I s	1.7 x 10 -10	67.6	0.14
	I w	6.4 x 10 -10	18.7	0.04
	I f	1.3 x 10 -9	13.7	0.02

By applying the principle of the magic number for Ru hcp metal cluster, the quantities of ligand previously obtained and the mean size of the particles (ca. 1.65 nm) determined by TEM

Table 3 .

 3 16 Determination of the number of ligands per RuNP and of the ratio of Ru surface atoms per ligand for each type of octanoic ligands surrounding the Ru x (C 7 H 15 COOH) 0.20 NPs

Type of interaction Ligand/Ru NP Ru surf /ligand Ligand/Ru surf

  According to the results, there is around 35 octanoic ligands (I s + I w + I f ) interacting for each 1.65 nm RuNP. Also, it was obtained an estimated number of ca.[23 -24] octanoate ligands strongly interacting with the RuNP surface (l s ). This value led to ca. 4.4 surface Ru atoms per ligand

	I s	Strong	23.5	4.4	0.22
	I w	Weak	6.5	16.1	0.06
	I f	Exchanging	4.8	21.8	0.04

  The surface mapping, obtained from the combined characterization techniques, offers a good approximation to the real state of the RuNP surface, the type of coordinated ligands, the variety of interactions in the hybrid material interface and the quantification of the different type of carboxylates bonded onto the Ru x (C 7 H 15 COOH) 0.20 NPs. However, to complete the characterization study is necessary to perform microanalyses. Ru x (C 7 H 15 COOH) 0.20 NPs (see section 6.1.3.2). These analyses were performed for a batch of purified NPs.Elemental analysis was performed aiming to corroborate if the added ligand (0.20 equiv.) remains in the sample or part of it was removed in the cleaning process (THF-pentane cycles). The results from this EA are shown in the table 3.17.

	CHAPTER III	Octanoic Acid-Capped RuNPs
	in
	Roberto González Gómez	227

3.2.5.3.2 Microanalyses applied to Ru x (C 7 H 15 COOH) 0.20 NPs

Elemental analysis (EA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) were performed to determine the carbon, hydrogen, nitrogen and ruthenium contents

Table 3 .

 3 17 C, H, N analysis of Ru x (C 7 H 15 COOH) 0.20 NPs.

	Element	Content (wt %)
	C	20.7
	H	2.9
	N	0.0

Table 3 .

 3 18 ICP-AES analysis of Ru x (C 7 H 15 COOH) 0.20 NPs.

	Element	Content (wt %)
	Ru	62.2

  the Ru x (C 7 H 15 COOH) 0.20 NPs by taking into account the RuNPs size obtained by TEM (ca. 1.65 nm), their crystalline structure (hcp) and the magic number for metal clusters.

	Roberto González Gómez	229

Scheme 3.9 Hydrides titration at the surface of Ru x (C 7 H 15 COOH) 0.20 NPs by the norbornene test. The obtained value was ca. 0.2 reactive hydrogens per ruthenium surface atom (0.2 H reac /Ru surf ) at r.t. Considering that there are ca. [100 -110 ruthenium surface atoms], this result leads to at least ca. 21 hydrogens per RuNP (21 H/Ru NP ). It is worthy to note that the number of hydrides per Ru surf is similar to that of octanoates (see table 3.15). Given the previous estimation of strongly coordinated ligands by NMR (ca. 23 -24 octanoates) and the hydride quantification (ca. 21), an approximated composition of the Ru x (C 7 H 15 COOH) 0.20 NPs can be proposed, as shown on scheme 3.10. Roberto González Gómez 230 Scheme 3.10 Approximated composition of Ru x (C 7 H 15 COOH) 0.20 NPs

  ). For example, both agreed to evaluate the surface composition of Ru x (CH 3 COOH) 0.40 NPs, to be around 0.4 ethanoates and [0.4 -0.6] hydrides per ruthenium surface atom. The minimum value in this last range was obtained from experimental techniques, assumed to underestimate the actual number of surface hydrides, and the second one by DFT calculations.It was concluded that the theoretical titration can be used to map the NPs surface or to Similar procedure, but based mainly in the theoretical titration, was performed for the Ru x (C 4 H 9 COOH) 0.30 NPs. A surface coverage value of 0.3 pentanoates and the same amount of hydrides per ruthenium surface atom has been foundThe surface mapping obtained for the Ru x (C 7 H 15 COOH) 0.20 NPs by NMR studies for coordinated ligands and norbornene test for hydrides quantification revealed numbers equal to ca. 0.2 octanoates and ca. 0.2 hydrides per ruthenium surface atom.

	CHAPTER III	Octanoic Acid-Capped RuNPs
	Roberto González Gómez	231

corroborate the experimental findings. Therefore, it is possible to obtain reliable theoretical data by using the Ru 55 NP model (see section 6.2.1), DFT-PBE energies, and the ab initio thermodynamics procedure (see section 6.2.6).

Table 3 .

 3 19 Optimized structures used for the Ru x (C 7 H 15 COOH) 0.20 DFT surface titration. The total number and coverage ratio of coordinated ligands and its corresponding DFT energy (eV) are also provided. (a) Number of hydrides coming from the dissociative adsorption of H 2 ; (b) total number of hydrides coming from a and from the C 7 H 15 COO-H bond dissociation.

Table 3 .

 3 20 Comparison between the experimental and theoretical surface coverage characterization of Ru x (C 7 H 15 COOH) 0.20 NPs.

	Approach

Octanoate (C 7 H 15 COO/Ru surf ) Hydrides (H/Ru surf )

	Experimental	0.2	0.2

Table 3 .

 3 21 Comparison between experimental and theoretical titrations of RuNPs stabilized by the studied carboxylic acid.

	RuNPs System	Quantity of ligand (equiv.)	Mean size (nm)	Experimental titration Carboxylate Hydrides (RCOO/Ru surf ) (H/Ru surf )	Theoretical titration Carboxylate Hydrides (RCOO/Ru surf ) (H/Ru surf )
	Ru x (CH 3 COOH) 0.40	0.40	1.51	0.3	0.3	0.4	[0.4 -0.6]
	Ru x (C 4 H 9 COOH) 0.30	0.30	1.47	---	---	0.3	0.3
	Ru x (C 7 H 15 COOH) 0.20	0.20	1.65	0.2	0.2	[0.2 -0.3]	[0.3 -0.6]

Table 3 .

 3 22 Estimated quantities of the different type of interacting ligands in the Ru x (C 7 H 15 COOH) 0.20 NPs determined by DOSY NMR data.

	Ligand

added (equiv.) Total ligand (equiv.) I s (C 7 H 15 COOH/Ru NP ) I w (C 7 H 15 COOH/Ru NP ) I f (C 7 H 15 COOH/Ru NP )

  When looking at the weakly coordinated ligands (I w ), it can be seen that it is possible to allocate one or two extra molecules which are in an outer shell of the RuNPs. This assumption can

	CHAPTER III				Octanoic Acid-Capped RuNPs
	0.00	0.20	23.5	6.5	4.8
	0.05	0.25	25.0	7.1	11.5
	0.10	0.30	23.2	8.6	20.4
	0.15	0.35	21.8	8.8	30.2
	0.20	0.40	20.7	7.7	41.1
	Roberto González Gómez				241

be observed by the increasing trend of this type of ligand, till is stabilized around eight carboxylates per RuNP. In other words, this shell was not completely full. According to this result,

Table 3 .

 3 23 Hydrodynamic diameters vs the extra-ligand added for preformed Ru x (C 7 H 15 COOH) 0.20 NPs.

	Ligand added (equiv.)	Total ligand (equiv.)	Hydrodynamic diameter I s I w (nm) (nm)
	0.00	0.20	3.8	1.04
	0.05	0.25	4.0	0.79
	0.10	0.30	4.3	0.74
	0.15	0.35	4.0	0.70
	0.20	0.40	4.1	0.69

  other words, it can be assessed that the Ru x (C 7 H 15 COOH) 0.20 NPs have less quantity of free ruthenium surface sites in comparison with PVP-and dppb-stabilized RuNPs and that CO molecules can only interact with the metal surface on edges or apexes.

	CHAPTER III	Octanoic Acid-Capped RuNPs
	Roberto González Gómez	248

All together the experimental and theoretical findings provide a precise surface mapping of the Ru x (C 7 H 15 COOH) 0.20 NPs. It was estimated certain quantities of coordinated octanoates and

  RuNPs, the hydrogen adsorption energy (ΔE H ) was calculated in five different sites at the surface of the Ru 55 (C 7 H 15 COO) 14 (H) 14 NP. Again, the chosen sites were the (001) and (101) planes, as well as the periphery of the added apex (B 4 & B 5 zone) which involve different type of interactions (see section 6.2.1). The ΔG H values are reported in figure3.50 and in section appendix E.3

	CHAPTER III	Octanoic Acid-Capped RuNPs
	Roberto González Gómez	250

Table 3 .

 3 It is possible to compare these energies of the HER evaluation with previous data obtained for the Ru x (CH 3 COOH) 0.40 and Ru x (C 4 H 9 COOH) 0.30 NPs, for which the same procedure was performed on the basis of the most stable DFT structure found for each nanosystem.All the data obtained for the H 2 dissociative adsorption Gibbs free energy (ΔG H ) in the three different models are summarized in table3.24. It can be observed that there is not a global direct trend because the found values depends on the nature of the analyzed sites. Therefore, it is necessary to analyze them by the type of adsorption sites. ΔG H in the (101) plane is lower for Ru x (CH 3 COOH) 0.40 that represents the faces of the RuNPs, whereas in the case of edges and apexes (plane (001) & B 4 -B 5 sites), ΔG H is lower for Ru x (C 4 H 9 COOH) 0.30 NPs. 24 H 2 dissociative adsorption Gibbs free energy (ΔG H ). Comparison by different Ru 55 NP sites of Ru 55 (CH 3 COO) 16 (H) 16 , Ru 55 (C 4 H 9 COO) 14 (H) 14 and Ru 55 (C 7 H 15 COO) 14 (H) 14 models.

	x (C 7 H 15 COOH) 0.20 NPs are promising

CH 3 COO) 16 (H) 16 Ru 55 (C 4 H 9 COO) 14 (H) 14 Ru 55 (C 7 H 15 COO) 14 (H) 14

  Ru x (C 7 H 15 COOH) 0.20 NPs could also be interesting catalysts owing to the good compromise between the number of available active sites (edges and corners) and the ΔG H criterion. It is noteworthy to observe that the carboxylic acid alkyl chain length has an influence, both on the stability of RuNPs

	CHAPTER III			Octanoic Acid-Capped RuNPs
	(001)	-2.5	-4.8 & -0.6	-2.5 & -5.3
	(101)	-2.3, -1.9 & 2.4	-7.8 & -4.8	-11.2 & -7.2
	B 4 & B 5	-7.9	0.8	-1.4
	(the most stable system is Ru x (C 7 H 15 COOH) 0.20 , in terms of added ligand quantity), and on the
	catalytic property regarding HER (the best system seems to be Ru x (C 4 H 9 COOH) 0.30 ). Therefore, it
	can be said that for this catalytic reaction it is necessary to find one system that exhibits the best
	compromise in terms of stabilization, of available active sites and on ΔG H adsorption energies, such
	as the pentanoate-stabilized RuNPs
	Roberto González Gómez		252

In summary, according to the ΔG H descriptor, none of these RuNPs appears clearly to be the best nanocatalysts for HER, although Ru x (C 4 H 9 COOH) 0.30 NPs seem to be slightly more promising due to its ΔG H value in the B 4 -B 5 site. Another interesting trend is that the turn-over could be increased in Ru x (C 4 H 9 COOH) 0.30 NPs, owing to the higher number of active sites.

  Roberto GonzálezGómez 254 DFT titration over the Ru 55 NP model, where a similar trend was found: hydrides [0.3 -0.6]/Ru surf and octanoates [0.2 -0.3]/Ru surf . These results highly agree with the experimental titration, showing once more the potentiality of these model to describe small RuNPs In comparison with other DFT titrated RuNPs, pentanoic -0.3 H/Ru surf & 0.3 C 4 H 9 COO/Ru Surf and ethanoic -[0.4 -0.6] H/Ru surf & 0.4 CH 3 COO/Ru Surf , it can be observed a direct trend. Longer the carboxylic alkyl chain length, the lesser quantity of ligand will be needed to stabilize similar size of RuNPs. Similar behavior was observed experimentally. From DOSY analyses, it was observed that probably the surface of the RuNPs was not completely crowded in both, the inner and outer shell, because it was found that each 4.4 Ru surf one octanoate is present. Therefore, a study on the Ru x (C 7 H 15 COOH) 0.20 NPs saturation was

	Also, by NMR and FTIR studies, it was noticed that the RuNPs were stabilized by the
	deprotonated carboxylic moiety (octanoates) without the presence of any excess, meaning that no
	free ligand was found. Similar behavior was observed for RuNPs stabilized by ethanoic and
	pentanoic acid, were it was found that they lie onto the RuNP surface as carboxylates due to the
	low energy activation of the O-H bond.
	Following with the characterization, it was possible to quantify the number of octanoates
	and hydrides surrounding the Ru x (C 7 H 15 COOH) 0.20 NPs by using deep NMR studies ( 1 H, DOSY &

Ru x (C 7 H 15 COOH) 0.20 NPs were fully characterized.

The Ru x (C 7 H 15 COOH) 0.20 NPs, analyzed by HRTEM and WAXS, showed to be a highly crystalline sample with a hcp crystalline structure. Previous experiments performed on the Ru x (CH 3 COOH) 0.40 NPs, showed a poorly crystalline sample. Thus, it was observed that RuNPs display better homogeneity and crystallinity, if they are synthetized with carboxylic moieties with longer alky chain length.

NOSESY NMR) and catalytic analysis (norbornene reduction). As a result, it was observed that there are 0.2 octanoates per Ru surf and 0.2 hydrides per Ru surf . A parallel study was performed by a performed. It was observed that the addition between [0.05 & 0.10 equiv.] of extra ligand is the optimal quantity of octanoic acid needed to cover the outer shell of the RuNPs. However, it was also noticed that the Ru x (C 7 H 15 COOH) 0.20 NPs has a completed inner shell and it suffers no modifications, even when 100 % more of stabilizing agent was added. The presence of ligand that do not take part of a fast exchange with weakly bonded ligand at the NPs surface was observed in the last part of the experiment, when 0.20 equiv. more of ligand (Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs) was

  with RuNPs stabilized by pentanoic acid (Ru x (C 4 H 9 COOH) 0.30

CO deposition.

Also, this last data was compared with previously obtained results for the HER reaction on other optimal RuNPs stabilized by ethanoic (Ru 55 (CH 3 COO) 16 (H)

16

) and pentanoic acid (Ru 55 (C 4 H 9 COO) 14 (H)

14

). As a result, it was observed that the best conditions for the HER reaction Roberto González

Gómez 255

are obtained

Table 4 .

 4 1 Diffusion coefficients of octanoic acid and benzoic acid moieties and corresponding signal weight for each addition of benzoic acid to colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 NPs.

	Benzoic acid added (equiv.)	D s (m 2 .s -1 )	Octanoic acid region Weight D w Weight (%) (m 2 .s -1 ) (%)	D s (m 2 .s -1 )	Benzoic acid region Weight D w Weight (%) (m 2 .s -1 ) (%)
	0.00	1.5x10	-10	66.2	6.1x10 -10	33.8	---	---	---	---
	0.10	1.8x10	-10	42.9	9.1x10 -10	57.1	1.9x10 -10	41.0	1.0x10 -9	59.0
	0.20	1.7x10	-10	37.8	9.4x10 -10	62.2	1.8x10 -10	22.8	1.1x10 -9	77.2
	0.30	2.1x10	-10	31.8	1.0x10 -9	68.2	2.1x10 -10	12.5	1.1x10 -9	87.5
	D OcAc = 1.3 x 10 -9 m 2 .s -1 ; D BAc = 1.4 x 10 -9 m	2 .s -1 ; s = strongly and w = weakly interacting ligand
	The enlisted data in the previous table describe several phenomena. First, the value of the
	diffusion coefficient of the strongly bonded ligand (D

s ), in the alkyl region and thus corresponding to the octanoic acid, remained quite similar ([1.5 to 2.1 x10 -10 m 2 .s -1 ]). While, the same variable but for the benzoic acid, displays similar value ([1.8 to 2.1 x10 -10 m 2 .s

-1 ]

). This indicates that the RuNPs CHAPTER IV Octanoic Acid vs Benzoic Acid Roberto González Gómez 272

Table 4 .

 4 2 Mapping of the RuNPs surface after ligand exchange experiments between octanoic and benzoic acid.

	Benzoic acid		Octanoic acid molecules			Benzoic acid molecules
	added
	(equiv.)	I s	I w	I f	I s	I w	I f
	0.00	23.5	6.5	4.8	---	---	---
	0.10	14.9	6.5	13.2	7.1	3.1	7.1
	0.20	13.1	6.2	15.2	7.9	6.1	20.8
	0.30	11.1	4.8	18.6	6.5	10.5	35.0
	s= strongly interacting ligand; w= weakly interacting ligand; f = "free" exchanging ligand.

2 and 0.3 equiv. of benzoic acid. This may indicate that only a certain quantity of ligands can be exchanged at the surface of the RuNPs, probably up to the surface saturation, and then, the added ligand in excess, either remains free in solution or exchanges with coordinated ones.

By taking into account the mean size of the Ru x (C 7 H 15 COOH) 0.20 NPs (ca. 1.65 nm), the crystallinity (hcp), the magic number for metal clusters rule and the extracted data from DOSY analyses (diffusion coefficients and corresponding contributions), the quantity of ligands laying at RuNPs surface can be estimated in order to get a surface mapping for each addition step (see section 6.1.3.7.2). The obtained data are reported in table 4.2

  DFT analyses were carried out by taking into account the DFT capped ligand titration previously described for Ru x (C 7 H 15 COOH) 0.20 NPs (see section 3.2.5.3.4). In this study, the Ru 55 (C 7 H 15 COO) 14 (H) 14 NP was found to be a stable composition at the experimental conditions range p, [C 7 H 15 COOH]. But, due to technical issues two slightly less crowded Ru 55 NP (Ru 55 (C 7 H 15 COO) 10 (H) 10 and Ru 55 (C 7 H 15 COO) 12 (H) 12 ) were used in order to study the viability of the ligand exchange.

Owing to the aim of the studies, two Ru 55 NP models with a combination of octanoates and benzoates as capping ligands were built and optimized (Ru 55 (C 7 H 15 COO) 3 (C 7 H 15 COO) 8 (H) 11 & Ru 55 (C 7 H 15 COO) 5 (C 7 H 15 COO) 8 (H) 13 ). The coordinates of the obtained structures are reported in section appendix F. The ligand exchange proposed reactions are presented on figure 4.12.

Table 4 .

 4 3 DFT energies obtained for ligand exchange reactions between octanoic and benzoic acid onto Ru 55 NP.

		DFT optimized structure energies		DFT reaction energy
		(eV)			(kcal.mol	-1 )
	Ru55(C7H15COO)10(H)10 + 8 C6H5COOH  Ru55(C7H15COO)10-m(C6H5COO)8(H)18-m + m C7H15COOH
	-1902.94	8*(-98.87)	-1970.43 -1676.49	5*(-145.87) 7*(-145.87)	-135.65 -85.02
	Ru55(C7H15COO)12(H)12 + 8 C6H5COOH  Ru55(C7H15COO)12-m(C6H5COO)8(H)20-m + m C7H15COOH
	-2197.64	8*(-98.87)	-1970.43 -1676.49	7*(-145.87) 9*(-145.87)	-67.46 -16.84

Table 4 .

 4 4 Average adsorption energy in Ru 55 NP covered by octanoates and a mixture of capped ligands.

				Ru 55 NP covered by
	Carboxylates species	Octanoates	Octanoates & Benzoates
		(kcal.mol	-1 )	(kcal.mol	-1 )
	11	-44.8		-49.3
	13	-44.1		-45.7

Table 4 .

 4 5 Diffusion coefficients of octanoic acid moieties and corresponding signal weight for the addition of TFA to a colloidal suspension of Ru x (C 7 H 15 COOH) 0.20 + 0.20 NPs.

	OcAc

added (equiv.) TFA added (equiv.) Octanoic acid region

  50.0 % of strongly attached ligand evidences the release of the moiety to the outer shell or to the reaction medium.

	D s (m 2 .s -1 ) 1.5x10 -10 1.6x10 -10 3.4x10 -10 ; s = strongly and w = weakly interacting ligand Weight (%) 0.00 66.2 0.20 29.8 0.20 0.10 15.9 -1 .s 2 -9 m D OcAc = 1.3 x 10 In the previous table, it can be observed the decrease of the strongly coordinated ligand D w (m 2 .s -1 ) Weight (%) 6.1x10 -10 33.8 9.6x10 -10 70.2 1.4x10 -9 84.1 Octanoic Acid vs TFA contribution (D CHAPTER IV of almost ca.
	Roberto González Gómez	291

s ), meanwhile the quantity of weakly bonded species increases (D w ). The decrease

Table 4 .

 4 6 DOSY NMR data extraction of the quantity of different type of interacting ligands in the Ru x (C 7 H 15 COOH) 0.20 +0.20 NPs.

	OcAc added	TFA added	Is	Iw	If	Is	Iw
	(equiv.)	(equiv.)	(OcAc/Ru NP )	(OcAc/Ru NP )	(OcAc/Ru NP )	(TFA/Ru NP )	(TFA/Ru NP )
	0.00	---	23.5	6.5	4.8	---	---
	0.20	---	20.7	7.7	41.1	---	---
	0.20	0.10	12.3	1.8	50.0	13.0	4.3
	A representation of this surface mapping is given in figure 4.16 that illustrates the ligand
	exchange between octanoic acid and TFA.

Table 4 .

 4 7 Comparison of the ligand exchange reaction depending on the nature of the incoming ligand, namely benzoic acid or trifluoroacetic acid. The data correspond to the addition of 0.10 equiv. of each incoming ligand.

	Ligand added	pKa	OcAc released (# molecules)	# Ligand incorporated (# molecules)	Ligand exchange ratio (OcAc r /A i )	Added ligand surface coverage (%)
	BAc	4.2	10.4	7.1	1.46	40.57
	TFA	0.2	8.4	13.0	0.64	51.38

  The obtained adsorption energy is ca. -89.3 kcal.mol-1 , which is ca. 10 kcal.mol -1 more than that for PS1 (see section appendix B.5). From this value, one can assume that each carboxylate unit of the PS3 stabilizes the Ru 55 NP with ca. -44.6 kcal.mol -1 , which is still weaker than the adsorption energy of ethanoic acids in the same NP model (ca. -50.6 kcal.mol -1 ). carboxylate vs PS3) could be achieved. It could however be favored if the preformed particles are stabilized by carboxylates with longer alkyl chain The last complex, PS4, interacts differently than PS2, showing interaction with the NP surface only via the carboxylates. The corresponding adsorption energy is of ca. 106.4 kcal.mol-1

	CHAPTER V	DFT Calculations PS onto Ru NP
	exchanging ligands (
	However, the difference observed in adsorption energies are getting smaller (from PS1 to
	PS3) and adsorption energies should be even closer to each other with RuNPs stabilized by
	carboxylic acids bearing longer alkyl chains (less adsorption energy ethanoic vs octanoic acid|).
	Roberto González Gómez	310

Mind that since it was compared, adsorption energies of carboxylates with dissociative adsorption energies on carboxylic acids, it is not easy to conclude whether an equilibrium between

Table 5 .

 5 1 provides a comparison of the adsorption energies calculated for the interaction of PS1, PS2 & PS4 with Ru 55 NP of low and intermediate surface coverage as described in figure 5.6(see section appendix B.6 and its coordinates in appendix F). It can be observed that for all cases, the adsorption energy values are lower at higher Ru 55 NP surface coverage (10 ethanoates vs 2 ethanoates). This is not surprising given that an increase of capping ligands tend to reduce the whole surface energy. It is important to point out that this coverage degree for the NPs is more alike the experimental conditions.

Moreover, all PS show higher adsorption energies than that of two ethanoic species in the same conditions. These results indicate that it is highly probable that for RuNPs with intermediate surface coverage, a ligand exchange between ethanoates and PS will be achieved, if the exchange is one to one carboxylate. Again, the ligand exchange reaction appears to be more favorable with PS4

Table 5 .

 5 1 Comparison of adsorption energies for different PS onto Ru 55 NP with low and intermediate surface coverage with that of two ethanoates in the same conditions.

	Preformed RuNPs	2 (CH 3 COOH)	Adsorption energy (kcal.mol -1 ) PS1 PS2	PS4
	Ru

55 (CH 3 COO) 2 (H) 2

	-101.16	-77.84	-175.50	-106.35

Ru 55 (CH 3 COO) 10 (H) 27

  .2 kcal.mol -1 lower for an intermediate surface coverage (Ru 55 (CH 3 COO) 10 (H)27 ) than for a less crowded Ru 55 NP (Ru 55 (CH 3 COO) 2 (H) 2 ). This indicates that the difference in Ru 55 NP surface coverage does not have a big impact on the adsorption energy of PS1. This can be attributed to the coordination angle of the pincer ligand. This is probably because this PS interacts with the metal surface via only one oxygen atom of each anchoring group. Moreover, on Ru 55 (CH 3 COO) 10 (H) 27 , the adsorption energy of PS1 is ca. 6.2 kcal.mol -1 more stable than the adsorption strength of two For Ru 55 (CH 3 COO) 10 (H) 27 model, PS2 shows also a better stabilization than the ethanoates and even higher than PS1. But as already observed PS2 interacts with the Ru 55 NP surface via the whole bipyridine ligand and not only via the anchoring groups (figure5.6 b). If such π coordination can occur at the surface of actual RuNPs, it could favor ligand exchange.Finally, PS4 displays the highest stability. But the adsorption energy is affected by the surface coverage as seen by the reduced value of ca. 16 kcal.mol -1 between Ru 55 (CH 3 COO) 2 (H) 2 to (Ru 55 (CH 3 COO) 10 (H) 27 ) models. PS4 has an adsorption energy similar to that observed with PS2, but only due to the σ coordination of carboxylate moieties. This means that the presence of CH 2

	CHAPTER V		DFT Calculations PS onto Ru NP
	-67.40	-73.63	-88.15	-90.95
	The adsorption energy of the more rigid photosensitizer (PS1; figure 5.6 a) is ca.
	ethanoates moieties
	Roberto González Gómez			313

4

Table 5 .

 5 2 DFT reaction energies for the ligand exchange reaction between Ru 55 (CH 3 COO) 12 (H) 29 NP and PS1 & PS4.

	DFT optimized structure energies (eV)	DFT reaction energy (kcal.mol -1 )

Ru 55 (CH 3 COO) 12 (H) 29 + PS1  Ru 55 (CH 3 COO) 10 (PS1)(H) 27 + 2 CH 3 COOH

	-1072.83	-453.44	-1433.54	2*(-46.50)	-6.23

Ru 55 (CH 3 COO) 12 (H) 29 + PS4  Ru 55 (CH 3 COO) 10 (PS4)(H) 27 + 2 CH 3 COOH

  The examined ligand exchange reactions are only another way to interpret the adsorption energies obtained for the PS coordination onto Ru 55 NP at intermediate surface coverage ratio. It can be clearly observed that the incorporation of a PS onto Ru 55 (CH 3 COO) 12 (H) 29 is possible by removing two ethanoic moieties. These results can be compared with those previously obtained when studying the DFT reaction energy for the ligand exchange between octanoic and benzoic

	-1072.83	-486.57	-1467.42	2*(-46.50)	-23.55

acids (see section 4.2.3). In those cases, the obtained DFT reaction energy was also directed towards a spontaneous reaction but much more efficient.

As a preliminary conclusion, the results obtained evidence that a ligand exchange between ethanoates and [Ru(bpy) 3 ] 2+ type complexes containing carboxylic acids groups can be performed onto RuNPs at an intermediate surface coverage ratio, provided that ethanoate moieties recombine with protons. At this point of our studies, the strategy (ligand exchange) envisaged in order to incorporate a PS onto RuNPs to get hybrid nanocatalysts looks to be appropriate and achievable, at least if the stabilization of the preformed NPs is performed with ethanoic acid.

Table 5 .

 5 3 Comparison of adsorption energies for PS1 onto different Ru 55 NP models (at low, intermediate and high surface coverage ratio) with that of two ethanoates in the same conditions. It can be observed that the PS1 adsorption energy dropped of ca. 15 kcal.mol -1 between intermediate (Ru 55 (CH 3 COO) 10 (H) 27 ) and high (Ru 55 (CH 3 COO) 14 (H) 31

	Preformed system	Moieties adsorption energy (kcal.mol -1 ) 2 (CH 3 COOH) PS1
	Ru 55 (CH 3 COO) 2 (H) 2	-101.16	-77.84
	Ru 55 (CH 3 COO) 10 (H) 27	-67.40	-73.63
	Ru 55 (CH 3 COO) 14 (H) 31	-65.83	-58.72

Table 5 .

 5 4 DFT reaction energy for the ligand exchange reaction between Ru 55 (CH 3 COO) 16 (H) 33 NP and PS1

	DFT optimized structure energies (eV)	DFT reaction energy (kcal.mol -1 )

Ru 55 (CH 3 COO) 16 (H) 33 + PS1  Ru 55 (CH 3 COO) 14 (PS1)(H) 31 + 2 CH 3 COOH

	-1264.48	-453.44	-1624.61	2*(-46.50)	7.11

Table 6 .

 6 1. Different quantities of ligand used for RuNPs synthesis.

		Molar equivalents of ligand per ruthenium precursor
	Ligand	RCOOH/[Ru]
		(equiv.)
	CH 3 COOH	0.20, 0.40
	C 4 H 9 COOH	0.05, 0.20, 0.30, 0.40, 0.50, 0.60
	C 7 H 15 COOH	0.10, 0.15, 0.20, 0.30, 0.40

Table 6 .

 6 2 Benzene and THF viscosity in relation with their temperature.

	([305],[306]) Benzene	T (K) 293 298 323	η (mPa.s) 0.649 0.604 0.436	THF [325]	T (K) 298 308 318	η (mPa.s) 0.463 0.428 0.390

  𝐼 [0] = 𝑋 𝐼 𝑠 + 𝑋 𝐼 𝑤 𝐷 𝐼 𝑤 = (𝑋 𝐼 𝑤 )(𝐷 𝐼 𝑠 ) + (𝑋 𝐼 𝑓 ) (𝐷 𝐼 𝑓 )

	𝑋 𝐼 𝑤 = 1 -𝑋 𝐼 𝑠 -𝑋 𝐼 𝑓
	𝑋 𝐼 𝑓 =	(𝐷 𝐼 𝑤 ) + (𝐷 𝐼 𝑠 )(𝑋 𝐼 𝑠 -1) (𝐷 𝐼 𝑓 ) -(𝐷 𝐼 𝑠 )

Ru surf Coverage THF/Ru NP THF coordination site or plane E DFT (eV) E ads (kcal.mol

  Adsorption of a Single Ethanoic Moiety (CH 3 COOH/ CH 3 COO) onto Ru 55 NP A.2.1 Adsorption of Ethanoic Acid on different Ru 55 NP SitesTable A.2 Ru 55 NP adsorption site of ethanoic acid, CH 3 COOH coordination mode, DFT energy of the optimized structure and ethanoic acid adsorption energy. Adsorption of Ethanoate on a Ru 55 NP Single Site Table A.3 Ru 55 NP adsorption site of ethanoate, (CH 3 COO) coordination mode, DFT energy of the optimized structure and ethanoate adsorption energy. Adsorption of Ethanoic Acid onto Hydrogenated Ru 55 NP Table A.4 Hydrogen coverage ratio, Ru 55 NP adsorption site of ethanoic acid and coordination mode, DFT energy of the optimized structure and ethanoic acid adsorption energy. Adsorption of THF onto Hydrogenated Ru 55 NP Table A.5 Hydrogen and THF coverage ratio, THF adsorption site in η mode, DFT energy of the optimized structure and THF mean adsorption energy. Table A.6 Ethanoate & hydrogen coverage ratios, (CH 3 COO) & H coordination modes, DFT energy of the optimized structure and carboxylic moiety mean adsorption energy.

				Carboxylic Moiety Adsorption Energies
	.2 0.4 0.8 1.2 1.6 A.3 Adsorption of Ethanoic Acid and THF onto 7 μ 2 μ 3 -460.48 -14.44 9 μ 8 μ 3 -492.69 -14.61 18 μ 17 μ 3 -564.41 -14.20 2 η 31 μ 19 μ 3 19 μ 4 -634.19 -13.23 8 η 43 μ 19 μ 3 -697.69 -11.98 Hydrogenated Ru 55 NP 3 Apex, (101), (001) -915.20 -12.25 4 Apex, (101), (001), corrugated surface No converged, led to spontaneous decoordination of one THF A.4 Adsorption of Ethanoate onto Hydrogenated and 1 μ 4 1.7 3 μ 6 η 50 μ 17 μ 3 -840.62 -26.36 0.1 4 μ 2 μ 2 μ 3 -618.99 -49.68 A.2 NP site CH 3 COOH coordination mode E DFT (eV) E ads (kcal.mol -1 ) B 4 μ -471.66 -18.22 (001) π -471.91 -23.80 (101) η-(O) -471.72 -19.57 Corrugated surface η-(O) -471.38 -11.77 (101) η-(OH) -471.06 -4.26 (101) μ -471.57 -16.15 Corrugated surface η-(O) -471.49 -14.13 Apex η-(OH) -471.38 -11.65 (CH 3 COO) coordination mode E DFT (eV) E ads (kcal.mol -1 B 4 μ -473.26 (001) μ -473.61 (101) μ -473.38 -57.90 Corrugated surface η-(O) -472.51 -37.81 1.2 3 Apex, (101), (001) -852.41 -17.73 4 Apex, (101), (001), corrugated surface -924.49 -13.90 1 Apex -770.39 -16.88 2 η 3 0.9 14 μ 3 1 μ 3 23 μ -708.14 -32.57 2 μ 1 η -63.01 2 Apex, (101) -779.91 -20.53 17 μ 3 -54.95 1 Apex -707.08 -21.23 1.6 2 μ 49 μ -793.09 -27.74 ) 0.8 1 Apex -637.128 -17.04 2 Apex, (101) -709.67 -15.21 3 Apex, (101), (001) -782.32 -15.36 4 Apex, (101), (001), corrugated surface -854.56 -13.08 2 1.3 2 μ 1 η 36 μ 17 μ 3 1 μ 4 -729.60 -27.78 6 η 8 A.2.2 NP site Bare Ru 55 NP 4 0.4 4 μ 12 μ 5 μ 3 -670.85 ---------0.9 2 μ 2 μ 3 2 η 22 μ 15 μ 3 -756.37 -34.37 A.3.1 Coverage H/Ru surf CH 3 COOH coordination mode E DFT (eV) 1 η E ads (kcal.mol -1 ) 0.8 Apex η-(OH) -611.68 -17.80 1.2 -681.52 -19.10 1.6 -745.31 Coverage (CH3COO)/Ru NP Coverage H/Ru Surf (CH 3 COO) & H coordination mode E DFT (eV) E ads (kcal.mol -1 1.3 4 μ 35 μ 3 -826.00 -33.53 20 μ ) 0.8 1 μ 4 1 μ 20 μ 3 -612.81 -43.84 8 η 16 μ -25.84 H/-1 ) 1.6 1 μ 8 η 46 μ 17 μ 3 -745.93 -40.12 0.8 1 μ 16 μ 3 1 μ 3 1 η 20 μ -660.00 -29.89 A.3.2 Coverage 1 1.2 1 μ 1.7 4 μ 48 μ -888.47 -27.59 2 η 3 18 μ 33 μ 18 μ 3 1 μ 4 -682.91 -51.11 7 μ 0.2 1 μ
	1.6	2 1.3	Apex, (101) 18 μ 3 3 μ 35 μ	-842.86 -777.89	-14.18 -32.33
	Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez				380 381 382 383

Table B .

 B 2 Octanoate & hydrogen coverage ratios, (C 7 H 15 COO) & H coordination modes, DFT energy of the optimized structure and octanoate mean adsorption energy.

	Coverage
	(C 7

H 15 COO)/Ru NP Coverage H/Ru Surf (C 7 H 15 COO) & H coordination mode E DFT (eV) E ads (kcal.mol

  Table B.3 Studied carboxylic moieties deposed onto the same adsorption site over the plane [100], DFT energy of the optimized structure and carboxylic moiety adsorption energy. Adsorption of PS onto Low Crowded Ru 55 NP Table B.5 DFT energy of the optimized Ru 55 (CH 3 COO) 2 (H) 2 structures interacting with different photosensitizer and its adsorption energy. Adsorption of PS onto Intermediate Crowded Ru 55 NP Table B.6 DFT energy of the optimized Ru 55 (CH 3 COO) 10 (H) 27 structures interacting with different photosensitizer and its adsorption energy.

	0.7 B.3 Adsorption of a Single Octanoic, Benzoic and 12 μ 2 μ 3 1 η 17 μ 11 μ 3 2 μ 4 -2556.30 -35.26 PS Ru NP E DFT E ads E ads /COO B.5 PS formula composition (eV) (kcal.mol -1 ) (kcal.mol -1 ) Trifluoroacetic Carboxylic Moiety onto Bare Ru 55 NP 1 [Ru(bpy) 2 (bpy(COO) 2 )] Ru 55 (CH 3 COO) 2 (PS1)(H) 2 -978.41 -77.84 -38.92
	2		[Ru(bpy)(bpy(COO)) 2 ]	Ru 55 (CH 3 COO) 2 (PS2)(H) 2	-982.86	-175.50	-87.75
	3	[Ru(bpy) 2 (bpy(CH 2 COO) 2 )]	Ru 55 (CH 3 COO) 2 (PS3)(H) 2	-1011.99	-89.25	-44.62
	4	[Ru(bpy)(bpy(CH 2 COO)) 2 ]	Ru 55 (CH 3 COO) 2 (PS4)(H) 2	-1012.78	-106.35	-53.18
	B.6 PS		Moiety Octanoate Octanoic acid Benzoate Benzoic acid Trifluoroacetate Trifluoroacetic acid formula PS	E DFT (eV) -572.35 -570.87 -525.79 -523.96 -474.54 -472.57 Ru NP composition	E DFT (eV)	E ads (kcal.mol -1 ) -48.64 -14.43 -58.77 -16.43 -59.43 -13.94 E ads (kcal.mol -1 )	E ads /COO (kcal.mol -1 )
	1	[Ru(bpy) 2 (bpy(COO) 2 )]	Ru 55 (CH 3 COO) 10 (PS1)(H) 27 -1433.54	-73.63	-36.82	-1 )
	0.2 [Ru(bpy)(bpy(COO)) 2 ] B.4 Adsorption of Combined Octanoates and Benzoates 7 μ 1 μ 3 5 μ 3 -1607.28 -45.92 2 Ru 55 (CH 3 COO) 10 (PS2)(H) 27 -1434.38 -88.15 -44.07 4 [Ru(bpy)(bpy(CH 2 COO)) 2 ] Ru 55 (CH 3 COO) 10 (PS4)(H) 27 -1467.42 -90.95 -45.48 3 μ 8 0.6 7 μ 1 μ 3 14 μ 11 μ -1673.39 -39.58 Moieties onto Bare Ru 55 NP 3 0.6 9 μ 1 μ 3 9 μ 3 -1968.13 -38.58 adsorption energy. 18 μ Table B.4 Octanoate, benzoate & H coverage ratios, DFT energy of the optimized structure and carboxylic mean 10 0.2 9 μ 1 μ 3 3 μ 3 -1902.94 -45.76 7 μ B.7 Adsorption of PS1 onto High Crowded Ru 55 NP
	Coverage (C 7 H 15 COO)/Ru NP	0.3 Coverage (C 6 H 5 COO)/Ru NP	11 μ 1 μ 3 Coverage 3 μ 9 μ 3 H/Ru Surf	E DFT -2197.64 (eV)	E ads -43.84 (kcal.mol -1 )
		12	5 3	0.7 8 8		10 μ 2 μ 3	0.3	20 μ 8 μ 3	-1970.43 -2262.33 -1676.49	-45.65 -36.86 -49.34
								1 μ 4
		14		0.3		13 μ 1 μ 3		9 μ 5 μ 3	-2493.46	-44.27
	Roberto González Gómez Roberto González Gómez					388 389

Table B .

 B 7 DFT energy of the optimized Ru 55 (CH 3 COO) 14 (H) 31 structures interacting with PS1 and its adsorption energy. Adsorption of Ethanoic Acid on Crowded Ru 55 NP Table C.1 Ethanoate & hydrogen coverage ratios, DFT energy of the optimized structure and ethanoic acid adsorption energy. Adsorption of THF on Crowded Ru 55 NP Table C.2 Ethanoate & hydrogen coverage ratios, DFT energy of the optimized structure and THF mean adsorption energy. Adsorption of THF on Crowded Ru 55 NP Table C.3 Ethanoate & hydrogen coverage ratios, DFT energy of the optimized structure and THF mean adsorption energy. Vibration Corrections for Ru-CH 3 COO onto Ru 55 NP Table D.3 Ethanoate coordination modes and their corresponding vibrational frequencies (Ru-COO) onto Ru 55 NP.

	APPENDIX C Coverage H/Ru Surf Coverage THF/Ru NP E DFT (eV) η 65, 120, 140, 220 & 555 D.3 Coordination mode C.3 Coverage (CH 3 COO)/Ru NP Vibrational frequencies (cm -1 ) APPENDIX E	E ads (kcal.mol -1 )
				0.3	μ	1 150, 205, 210, 230, 450 & 530 -1130.46	-48.79
		14		0.7	μ 3	1 170, 175, 190, 195, 215, 225, 370 & 490 -1193.92	-40.80
						2		-1218.37	-39.11
	Coverage E.1 Adsorption of Hydrogen on Ru 55 (CH 3 COO) x (H) y NP E DFT E ads C.1 Coverage Model.
		(CH 3 COO)/Ru NP	H/Ru Surf	(eV)	(kcal.mol -1 )
					0.3		-1105.03	-48.86
			14		0.7		-1167.49	-39.21
	C.2 Coverage		Coverage	Coverage		E DFT	E ads
	(CH 3 COO)/Ru NP	H/Ru Surf	THF/Ru NP		(eV)	(kcal.mol -1 )
	PS	14	PS formula	0.3	Ru NP composition 1 1	E DFT (eV)	E ads -1130.46 (kcal.mol -1 ) -1193.92	-48.79 E ads /COO (kcal.mol -1 ) -40.80
	1	[Ru(bpy) 2 (bpy(COO) 2 )] 0.7	Ru 55 (CH 3 COO) 14 (PS1)(H) 31 -1624.61 2	-58.72 -1218.37	-29.36 -39.11
	Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez						390 391 393 394

Table E .

 E 1 Ethanoate & hydrogen coverage ratios, H coordination site in μ mode, hydrogen adsorption energy and hydrogen Gibbs free energy. Adsorption of Hydrogen on Ru 55 (C 4 H 9 COOH) 14 (H) 14 NP Model.

	E.2 Table E.2 Pentanoate & hydrogen coverage ratios, H coordination site in μ mode, hydrogen adsorption energy and
	hydrogen Gibbs free energy.
	Coverage	Coverage	H coordination	E ads	ΔG H*
	(C 4 H 9 COO)/Ru NP	H/Ru Surf	site or plane	(kcal.mol -1 )	(kcal.mol -1 )
			B 4-5	-4.7	0.8
				-6.1	-0.6
	14	0.3	(001)	-10.3	-4.8
			(101)	-13.3	-7.8
				-10.3	-4.8
	E.3 Adsorption of Hydrogen on Ru 55 (C 7 H 15 COOH) 14 (H) 14
	NP Model.
	Coverage	Coverage	H coordination	E H*	ΔG H*
	(CH 3 COO)/Ru NP	H/Ru Surf	site or plane	(kcal.mol -1 )	(kcal.mol -1 )
			B 4-5	-14.6	-9.1
			(001)	-14.3	-8.8
	0	0		-15.6	-10.1
			(101)	-15.8	-10.3
				-12.3	-6.8
			B 4-5	-14.1	-8.6
			(001)	-14.1	-8.6
	1	1.2		-11.9	-6.4
			(101)	-3.5	2.0
				-6.5	-1.0
			B 4-5	-12.9	-7.4
			(001)	-8.0	-2.5
	16	0.2		-7.8	-2.3
			(101)	-3.1	2.4
				-7.4	-1.9
	Roberto González Gómez				395

Table E .

 E 3 Octanoate & hydrogen coverage ratios, H coordination site in μ mode, hydrogen adsorption energy and hydrogen Gibbs free energy.

	Coverage
	(C 7

H 15 COO) /Ru NP Coverage H/Ru Surf H coordination site or plane E ads (kcal.mol -1 ) ΔG H* (kcal.mol

  Ru 55 (CH 3 COO) 14 (H) 14 Ru 55 (CH 3 COO) 10 (H) 10 Ru 55 (C 7 H 15 COO)(H) Ru 55 (C 6 H 5 COOH) Ru 55 (C 6 H 5 COO)(H)

	71 72 145 55 1 89 105 55 31 183 85 1 9 1 109 57 209 11 163 103 255 407 83 235 1 153 Domain 40 -Ru 55 (CH 3 COO) 16 (H) 25 C 14.078 10.0737 C 21.8883 11.8908 H 10.5068 21.2588 Ru 17.9129 12.7177 Ru 14.9345 13.0475 H 9.4697 8.1123 H 20.6446 6.7784 7.0896 15.4721 6.8999 15.3928 16.7815 15.1318 19.3973 H 11.9401 19.3428 14.6219 H 13.5744 19.2266 15.0614 Ru 20.1957 8.5774 10.9301 Ru 12.4888 11.172 17.8651 H 9.1905 8.048 19.6313 O 18.2408 16.9893 14.4963 Ru 14.9639 13.5165 15.9732 Ru 14.8377 7.0298 8.8327 Ru 16.3074 4.7372 8.9741 Ru 11.4443 9.9106 13.0817 Ru 14.9092 13.4406 15.1112 H 15.8119 10.6710 17.4157 C 13.8982 20.5753 27.4871 H 26.3801 18.8665 10.6472 Ru 11.06700 13.43036 13.29836 H 16.75502 16.87341 11.07427 C 16.3355 13.9706 7.9386 H 7.0236 13.2546 15.9701 H 20.4504 25.7519 5.3808 C 4.1860 13.6154 14.8046 H 21.5219 5.7687 20.9120 Ru 19.4873 17.002 19.8187 H 18.6267 14.8295 26.2994 146 H 9.5559 20.1739 17.8173 56 C 12.7443 7.197 19.6787 2 Ru 15.1973 13.0265 11.1553 H 8.0913 8.7073 18.4246 106 H 11.1260 12.1452 18.2335 H 15.4176 17.8653 17.1489 56 H 9.2308 9.6575 8.6777 32 Ru 13.6323 13.4375 9.2791 184 H 15.9658 14.5853 7.9745 86 O 16.5295 8.7315 15.8977 2 Ru 15.0676 13.4069 11.6413 10 Ru 14.7967 11.6666 8.7891 Ru 14.6777 4.2834 11.1645 Ru 12.9103 12.3239 8.8892 2 Ru 14.9951 13.3712 10.7258 110 H 16.5744 9.5932 15.0594 58 C 14.2789 21.9244 28.0999 210 H 26.9907 18.5385 8.2435 12 Ru 8.46717 13.47038 13.31857 164 H 12.56894 7.98758 12.67185 104 C 9.1170 18.9523 30.6041 256 H 8.8796 14.5196 14.8052 408 H 22.1967 25.7833 5.6069 84 C 4.9830 13.7995 16.0992 236 H 19.2532 6.4687 20.0660 2 Ru 19.4838 16.8686 15.5182 154 H 17.2043 15.8921 26.2984	128 129 169 107 77 161 90 111 110 91 107 192 136 69 41 75 68 129 133 252 87 237 179 331 414 159 284 77 217 170 108 78 162 112 111 92 108 193 137 70 42 76 69 130 134 253 88 238 180 332 415 160 285 78 218	H H H C C H H H H H O H H C Ru 74 H H H O H H O H H H H C H H C H H H H O H H C Ru 75 H H H O H C H O H H H H C H	20.25 7.191 18.0697 14.9909 9.978 18.2338 21.4213 7.6725 12.1378 14.9245 12.8356 7.8939 9.6415 19.7583 10.2425 17.9954 7.1908 7.7943 17.4468 12.7022 8.9671 16.8120 15.7835 17.1534 9.4284 13.4573 17.0226 17.6301 3.5818 8.9842 9.728 8.8853 10.8508 9.949 11.8403 9.957 18.342 9.9405 12.9958 14.8773 7.071 15.2944 17.4936 H 7.1734 4.5795 H 14.9452 10.1437 3.4153 10.6398 9.9390 11.5867 7.7817 15.9515 12.9379 9.7606 5.8714 18.7325 13.2818 19.7111 14.1632 18.8747 8.3257 16.4979 23.71885 11.02939 16.93747 18.21254 19.73936 4.14116 21.9380 20.4483 18.5739 9.9810 11.3885 23.8397 19.9888 25.7421 9.7964 13.5226 16.1350 20.6258 6.8324 9.2558 15.6910 11.815 21.4826 12.9053 14.118 9.9008 3.8977 H 9.2797 14.3439 21.8414 16.3496 10.9104 9.0432 9.9985 15.0855 21.3151 16.846 20.7533 8.5012 18.1466 13.6914 16.9029 10.5615 15.8700 9.4307 18.8253 5.9171 4.9107 11.462 16.1705 19.6771 12.8607 22.369 11.9223 18.4318 11.5935 11.3701 13.7741 9.791 5.9374 16.2510 6.3155 6.7339 H 14.7006 10.0197 14.1102 11.7706 10.9978 9.3425 9.4475 18.0023 13.9436 10.2031 8.2767 18.8190 17.6438 10.3244 19.2042 19.6222 6.2166 17.6090 24.34528 11.64411 18.18972 16.57088 20.28625 3.75133 18.0527 10.5106 18.9998 12.3519 10.9585 24.5336 19.7935 23.2498 9.8236 17.5865 23.7909 16.2392 7.6986 7.9933 16.5611 3.3268 11.984 14.8842 14.1071 8.3941 4.8344
	73 147 57 3 107 57 33 185 87 3 11 3 111 59 211 13 165 105 257 409 85 237 3 155	C C Ru H H H H Ru H O Ru Ru Ru Ru H C H Ru H C H H C H Ru H	20.399 20.0880 12.7097 15.1605 12.427 15.1322 13.7105 12.5347 11.9365 17.6389 8.1851 11.4898 14.4158 14.5614 18.5604 15.1822 14.9418 18.5444 13.3827 7.905 7.7707 16.5701 15.8064 8.7676 13.7913 13.5393 17.8212 16.211 19.2843 6.7907 14.4768 7.759 16.1785 15.0385 11.9094 13.8631 13.4650 H 9.3088 8.7281 Ru 17.6335 7.2037 4.5495 11.5500 11.5548 11.0374 14.9413 11.8661 12.9514 17.7688 14.2337 9.9486 14.0499 19.0685 25.4298 25.6096 17.4460 8.0158 9.63125 15.63222 13.38578 16.53880 12.09496 8.32495 9.5049 18.4180 29.2247 8.3154 16.0178 15.5539 21.9015 26.9909 7.7890 6.2905 14.5719 15.9098 18.7429 6.8117 21.7184 19.5647 15.3762 17.7091 24.7118 19.4485 12.2422	130 171 109 79 163 113 112 93 109 194 138 71 43 77 70 131 135 254 89 239 181 333 416 161 286 79 219	H H C C H H H H O H H C Ru 76 H H H O H H O H H H H C H	7.4133 10.1583 16.6533 10.5063 11.2555 12.5713 12.2952 14.9387 16.4095 15.9151 8.8806 14.9003 8.4035 7.9528 20.2925 8.7909 21.9625 11.2028 19.9082 14.9991 7.8736 19.1672 4.4870 7.0412 10.377 14.178 19.7142 11.1895 21.9733 11.4114 18.1685 11.476 14.9635 13.7446 10.4747 7.2758 16.2924 H 6.3652 10.8866 H 16.2967 12.4906 3.5920 9.8688 10.3265 13.6281 7.9914 12.7175 11.8101 8.7517 8.6359 17.8292 19.1667 11.0999 17.7240 21.2365 6.8855 17.8361 21.65019 10.85434 15.46909 22.23829 11.10497 14.57004 19.4399 11.2412 17.3790 12.5444 9.8132 23.2091 21.5389 23.0862 9.9415 18.5850 23.8924 19.1635 9.3905 7.8670 14.7078 4.6204 12.7816 14.7139 13.0491 11.1129 5.8489
	-1 ) 8.4029 17.9023 396 11.473 15.6874 13.5489 15.4822 9.4523 11.4488 15.7253 17.8446 9.4058 13.7272 17.9153 11.524 15.9255 13.9563 11.7039 13.7873 15.8145 11.6228 15.9726 13.5476 13.5047 22.0748 20.5741 8.1052 8.9812 8.7994 9.3431 16.4143 15.756 14.1528 14.45 15.7867 15.36 5.5094 397 9.4663 15.9091 16.3413 17.4777 15.067 13.6594 13.4581 14.9136 16.2726 16.4874 4.9769 5.5817 4.959 11.6366 10.1301 9.8506 17.3183 9.9949 18.6207 17.2461 12.0203 14.5098 16.2583 15.6255 17.7052 9.5846 11.1041 10.8638 13.2839 20.182 19.6901 18.8136 8.5938 22.146 22.1783 21.6206 12.7106 7.4443 9.0051 8.6356 15.4463 18.0066 19.0549 19.5601 9.7646 12.2304 11.4605 10.5063 17.4034 4.7107 4.8389 4.816 10.4572 398 22.3859 13.2874 17.7156 19.1812 -1.4 -2.5 -5.3 -7.2 -11.2 15.7453 17.2985 17.3073 8.8908 7.9088 11.0713 10.3045 10.2593 11.1658 13.5423 13.4845 13.682 14.973 15.0613 8.921 10.4088 11.2163 10.5477 12.82 12.7507 10.019 10.7282 12.0058 12.1393 12.6983 12.7823 15.313 14.773 20.6885 19.45 17.6663 16.9463 4.9278 6.2452 9.506 15.0098 21.0253 21.4858 20.5023 17.8155 18.6233 17.0463 4.4148 4.2983 5.1145 9.621 8.4335 9.9878 14.5848 9.6607 17.013 14.9483 16.9395 16.6043 12.2795 10.9317 11.4845 11.2478 12.8943 13.2203 6.6153 6.4655 5.4513 17.0045 9.3505 7.7728 8.4545 14.7423 15.551 13.7908 14.9565 18.5127 19.0315 19.26 20.2585 8.1443 20.2745 19.0193 19.799 11.468 22.3338 21.8283 21.8265 9.8423 14.0423 15.8365 14.8605 9.362 11.1676 14.3891 9.5805 19.7545 20.488 6.6508 14.5571 APPENDIX F 0.3 B 4-5 -6.9 (001) -8.0 -10.8 (101) -12.7 -16.7 Roberto González Gómez 14 Domain 39 -Ru 55 (CH 3 COO) 16 (H) 16 1 Ru 15.0173 12.7465 15.8444 2 Ru 15.2427 12.6815 11.479 3 Ru 15.2188 11.1852 13.6687 4 Ru 13.5793 14.9275 15.7529 5 Ru 13.7098 14.9248 11.4439 6 Ru 12.355 12.4865 15.6907 7 Ru 13.806 13.4053 13.5866 8 Ru 12.503 12.541 11.3875 9 Ru 12.4648 10.9403 13.5567 10 Ru 12.311 15.6525 13.5429 11 Ru 11.1515 13.2263 13.4641 12 Ru 8.5093 13.0702 13.3949 13 Ru 9.639 15.299 13.5257 14 Ru 9.807 10.73 13.5083 15 Ru 10.671 17.6115 13.4664 16 Ru 11.126 13.0912 9.2869 17 Ru 9.8845 12.3163 11.4876 18 Ru 9.7368 12.3535 15.4744 19 Ru 10.8253 13.1545 17.6387 20 Ru 12.5203 15.7248 9.359 21 Ru 11.003 14.7175 11.3485 22 Ru 10.903 14.6848 15.5841 23 Ru 12.021 15.5583 17.8217 24 Ru 12.187 17.1855 11.5016 25 Ru 13.493 18.089 13.6282 26 Ru 12.028 17.0958 15.6333 27 Ru 11.4165 8.5947 13.5798 28 Ru 12.7105 11.0372 9.3267 29 Ru 11.297 10.1538 11.4265 30 Ru 11.2168 10.0693 15.6504 31 Ru 12.4268 10.9503 17.7515 32 Ru 13.8523 13.4278 9.3155 33 Ru 13.524 13.3988 17.8755 34 Ru 15.2138 15.605 9.4159 35 Ru 14.9925 15.8173 13.6102 36 Ru 14.6395 37 Ru 14.8343 38 Ru 14.507 39 Ru 14.0838 40 Ru 13.04 41 Ru 15.2413 42 Ru 13.943 43 Ru 13.8085 44 Ru 14.926 45 Ru 16.4413 46 Ru 16.483 47 Ru 16.09 48 Ru 16.3755 49 Ru 16.2095 50 Ru 16.5178 51 Ru 16.575 52 Ru 17.8725 53 Ru 16.4658 54 Ru 17.7705 55 Ru 17.6333 56 C 5.4263 57 C 6.755 58 C 14.1905 59 C 14.241 60 C 20.4808 61 C 19.259 62 C 7.3835 63 C 8.6818 64 C 9.6782 65 C 10.2235 66 C 19.1765 67 C 17.8872 68 C 16.3037 69 C 15.708 70 C 14.1753 Roberto González Gómez 74 C 9.0112 6.4407 10.6626 75 C 9.8503 7.5118 11.3082 76 C 9.0783 8.7008 19.3175 77 C 10.0303 9.3653 18.3586 78 C 10.0255 14.735 21.6369 79 C 10.5178 14.5887 20.2202 80 C 17.403 19.2575 8.5072 81 C 16.5248 18.228 9.1692 82 C 16.884 19.4395 18.6857 83 C 16.087 18.3608 18.0001 84 C 12.1135 21.6475 11.5099 85 C 12.3578 20.2132 11.9051 86 C 13.3845 14.8815 5.1589 87 C 13.4025 14.7865 6.6625 88 O 6.7223 12.0165 13.4802 89 O 7.8163 10.0167 13.4893 90 O 13.5355 13.0478 20.0273 91 O 14.9888 11.301 19.9412 92 O 18.1485 13.0903 8.3944 93 O 19.373 12.5638 10.2258 94 O 9.1623 15.3275 10.3862 95 O 9.2112 13.7708 8.7402 96 O 10.9705 18.6813 16.4614 97 O 9.9273 19.237 14.5306 98 O 16.9288 17.0477 13.6245 99 O 17.8413 16.2363 15.5238 100 O 14.5327 6.529 15.7812 101 O 16.4353 6.9798 14.6011 102 O 15.1723 10.2977 7.5306 103 O 12.9153 10.2643 7.4017 104 O 19.7055 12.636 16.002 105 O 19.902 11.261 14.2163 106 O 10.3398 7.2518 12.4727 107 O 10.0217 8.6088 10.6943 108 O 9.8018 9.3038 17.1135 109 O 11.0585 9.9543 18.8773 110 O 10.2253 13.505 19.6053 111 O 11.1695 15.5708 19.7148 112 O 16.183 18.4503 10.3836 113 O 16.1893 17.1943 8.4898 114 O 15.8485 17.294 18.654 115 O 15.683 18.5865 16.7986 116 O 11.9763 19.3045 11.0945 117 O 12.9245 19.998 13.0356 118 O 13.067 15.841 7.3151 119 O 13.7338 13.6715 7.1913 120 H 5.564 8.9363 13.6217 121 H 4.8558 10.2605 12.6396 122 H 4.8425 10.384 14.4032 123 H 15.1493 11.6375 22.4575 124 H 13.4173 11.2665 22.3343 125 H 13.9255 12.9615 22.5389 126 H 21.3105 12.2298 8.6437 127 H 20.774 13.7145 7.8029 131 H 6.563 132 H 8.7673 133 H 10.4332 134 H 9.4888 135 H 19.7615 136 H 18.97 137 H 19.7643 138 H 16.727 139 H 15.5523 140 H 17.13 141 H 13.2255 142 H 14.4115 143 H 14.9918 144 H 18.1323 145 H 16.2268 146 H 13.7073 147 H 10.3115 148 H 11.2968 149 H 13.2535 150 H 9.324 151 H 18.3125 152 H 22.3918 153 H 22.1068 154 H 22.265 155 H 17.8265 156 H 8.9282 157 H 8.0038 158 H 9.4383 159 H 9.0168 160 H 8.8948 161 H 9.5372 162 H 8.1385 163 H 11.3097 164 H 10.5482 165 H 10.1613 166 H 8.9478 167 H 14.9965 168 H 17.535 169 H 18.384 170 H 16.9705 171 H 11.3163 172 H 17.0808 173 H 17.829 174 H 16.3238 175 H 10.5348 176 H 12.5683 177 H 11.0308 178 H 12.5203 179 H 16.2258 180 H 13.9258 181 H 13.818 182 H 12.3395 183 H 12.6072 Roberto González Gómez 1 Ru 15.1519 12.6385 15.6818 2 Ru 15.1375 12.5719 11.4131 3 Ru 15.1478 11.0585 13.6018 4 Ru 13.7584 14.9056 15.7912 5 Ru 13.6393 14.8752 11.4318 6 Ru 12.4469 12.4701 15.7123 7 Ru 13.8169 13.3551 13.5782 8 Ru 12.4079 12.5107 11.4471 9 Ru 12.4097 10.8611 13.5995 Ru 12.4028 15.6600 13.6054 Ru 11.1449 13.1985 13.5853 Ru 8.5265 13.2080 13.5898 Ru 9.7137 15.3657 13.6531 Ru 9.7487 10.8006 13.6772 Ru 10.8423 17.6519 13.5878 Ru 10.9131 13.0872 9.4133 Ru 9.7875 12.3406 11.6301 Ru 9.7676 12.4586 15.6655 Ru 11.0237 13.2185 17.7235 Ru 12.3521 15.6223 9.3754 Ru 10.9784 14.7136 11.4610 Ru 11.0704 14.7336 15.6690 Ru 12.3162 15.5195 17.9125 Ru 12.1624 17.1720 11.4868 Ru 13.5752 18.0111 13.6011 Ru 12.3305 17.0908 15.7153 Ru 11.2447 8.6013 13.7084 Ru 12.4433 11.0186 9.3552 Ru 11.1569 10.1431 11.5054 Ru 11.1926 10.1238 15.7787 Ru 12.5931 10.9937 17.8466 Ru 13.7009 13.3520 9.2876 Ru 13.7522 13.3286 17.8416 Ru 15.0415 15.5903 9.1995 Ru 15.0066 15.6637 13.5139 Ru 15.0849 15.6131 17.8419 Ru 14.9549 17.1170 11.3932 Ru 14.9668 17.1648 15.6260 Ru 13.9402 8.7706 13.6148 Ru 12.7754 7.8852 15.5823 Ru 15.0089 11.0202 9.3098 Ru 13.8003 10.1962 11.3638 Ru 13.8046 10.2084 15.7338 Ru 15.1130 11.0530 17.7438 Ru 16.3142 13.3933 9.2542 Ru 16.4782 13.3608 13.5178 Ru 16.3366 13.3728 17.7576 Ru 16.2920 14.9216 11.2369 Ru 16.3822 14.9590 15.6454 Ru 16.3928 8.8363 13.5487 Ru 16.4525 10.2715 11.3856 Ru 17.8111 11.0137 13.4720 Ru 16.5608 10.4085 15.6488 Ru 17.7067 12.7533 11.3669 Ru 17.8241 12.5347 15.7453 C 5.3468 10.3022 13.0812 C 6.6958 10.9518 13.2617 C 15.2466 12.3318 21.8736 C 15.1362 12.6747 20.4132 C 20.2950 12.4322 7.8148 C 19.1213 12.5887 8.7446 C 7.1827 15.3773 9.1818 C 8.4986 14.7954 9.6298 C 9.7647 20.4460 16.7766 C 10.3501 19.2737 16.0360 C 19.1806 18.1083 14.5455 C 17.9538 17.3661 15.0080 C 16.2062 5.1891 15.2048 C 15.1578 6.2174 14.8995 C 13.6270 9.9127 5.3191 C 13.6362 10.2718 6.7790 C 21.8322 10.8161 15.1929 73 C 20.3876 148 H 19.1251 19.1631 14.8351 172 H 10.9710 58 C 19.7351 18.4379 15.7909 110 H 18.0322 4 Ru 13.4935 15.2238 15.4276 80 C 17.2898 H 10.549 15.8818 21.8262 164 H 17.144 108 H 12.7269 8.1792 13.4222 114 H 13.1278 H 14.1058 9.2374 11.4133 113 H 12.4475 18.5910 58 H 12.7527 3.2835 8.8072 94 H 20.6243 5.3408 8.9470 34 Ru 15.07 15.6178 9.1931 110 O 10.433 8.8385 17.2861 186 H 16.5255 20.3598 8.2033 195 H 12.516 21.7998 10.2513 88 O 18.474 14.0273 7.9386 139 H 15.9135 5.641 16.4559 4 Ru 13.5686 15.6981 15.9412 72 C 21.732 12.2896 15.5355 12 Ru 10.9423 9.4479 8.6740 44 Ru 17.5780 7.1446 12.9738 Ru 16.4062 6.2553 6.6980 77 H 16.0616 12.5128 13.9854 Ru 11.4837 11.5848 15.0204 78 H 11.8115 10.6218 16.8848 4 Ru 13.4942 15.6796 15.1909 71 H 9.0813 13.6820 16.4752 112 H 17.9368 12.1000 11.7573 132 H 18.1522 17.7120 17.9186 60 C 14.5266 18.8753 24.0034 136 O 15.0467 13.9508 22.6320 212 H 25.3326 19.1650 8.3573 255 H 21.1513 5.3773 15.8173 14 Ru 9.62977 11.09582 13.31275 90 C 20.21982 11.25882 15.17983 166 H 16.62687 10.28700 9.54756 240 H 21.66628 9.75275 15.52350 106 C 10.8597 18.9378 28.7378 182 O 18.7534 14.6345 10.6411 258 H 12.1460 3.2508 9.8203 334 H 12.2156 11.6283 21.5301 410 H 20.1532 26.9772 7.5656 417 H 21.5486 24.1898 12.1772 86 C 7.0627 14.7987 17.2120 162 H 16.4773 14.5576 14.8594 238 H 20.5457 8.5554 21.9186 287 H 8.5225 9.1210 13.8247 4 Ru 18.0597 19.1594 19.9033 80 C 5.4411 12.8884 16.0024 156 H 24.8784 17.8399 11.5733 220 H 13.0463 9.6191 6.781 14.9540 74 C 8.5548 6.6214 149 H 19.2194 18.0531 13.4470 173 H 9.5869 8.9300 20.5958 59 C 18.4243 17.7009 15.6663 111 H 16.5202 9.9118 16.8218 5 Ru 13.6088 15.283 11.0695 81 C 16.3695 18.7218 8.9983 H 10.0768 14.1422 21.8689 165 H 17.7845 19.2608 18.8672 109 H 16.4191 13.1204 7.8131 115 H 11.3973 6.9721 19.3562 H 13.8582 10.4965 9.1588 114 H 13.7929 19.3104 11.5781 59 H 18.3649 14.6233 6.1719 95 H 18.8036 5.8488 12.7305 35 Ru 14.9853 15.7948 13.4729 111 O 11.7138 9.589 18.9917 187 H 14.8817 20.1935 7.5551 196 H 16.2897 9.8253 17.1389 89 O 19.6123 13.3223 9.7625 140 H 16.3228 6.5745 17.9075 5 Ru 13.5311 15.6811 11.5794 73 C 20.2557 12.4635 15.3009 13 Ru 12.1542 11.5826 8.7994 45 Ru 18.6670 9.4612 4.5505 Ru 16.2282 6.3535 10.8754 78 H 17.4342 14.7205 7.8216 Ru 12.7681 12.1882 17.2753 79 H 12.8139 15.3704 7.7560 5 Ru 13.5285 15.8490 10.7427 72 H 10.4256 16.0036 9.0063 113 H 18.0109 13.6907 14.1417 133 H 18.9704 16.2413 17.3008 61 C 18.7332 14.8174 26.4831 137 O 13.8123 13.2742 20.8618 213 H 21.8984 23.9921 12.7555 256 H 19.9043 6.4102 15.0886 15 Ru 10.84006 17.91626 13.31798 91 C 19.04293 18.93624 12.90059 167 H 16.31312 11.89026 18.45467 241 H 21.66312 11.21029 17.59986 107 C 11.2474 18.4504 27.3392 183 O 16.4952 14.4788 10.7568 259 H 10.9765 3.8295 11.0243 335 H 11.8656 12.7878 22.8134 411 H 20.1421 24.4749 7.6030 418 H 19.8635 24.6333 12.0134 87 C 8.4143 15.4837 16.9988 163 H 15.1515 16.8690 23.0072 239 H 21.0773 8.1970 20.2759 288 H 8.9212 10.7370 15.7079 5 Ru 17.9869 19.1888 15.4865 81 C 6.7403 13.6829 15.84 157 H 11.836 19.6224 11.7508 221 H 15.56 9.5442 6.6697 10.9165 75 C 9.5122 7.6289 150 H 16.4997 4.6606 14.2896 174 H 8.5874 8.2166 19.2732 60 C 13.1668 8.4497 6.2224 112 H 16.2335 8.7629 14.7342 6 Ru 12.2615 12.7755 15.3806 82 C 16.88 19.6932 18.4205 H 8.934 15.3605 21.2745 166 H 16.281 20.1188 19.2382 110 H 16.7703 16.3316 9.3959 116 H 16.6172 17.3855 14.9735 H 15.2623 10.5790 18.7167 115 H 11.1058 12.6171 7.9525 60 H 10.4330 11.1993 8.8653 96 H 19.0171 4.5072 10.6370 36 Ru 15.1845 15.7843 17.7572 112 O 15.4305 18.7692 9.9281 188 H 11.1415 7.5638 14.9677 197 H 13.5673 14.0248 4.66 90 O 9.3195 16.3632 10.1312 141 H 17.4853 6.5225 16.5565 6 Ru 12.2372 13.3137 15.89 74 C 8.9543 7.2371 10.8133 14 Ru 12.1338 6.9729 8.6376 46 Ru 18.9188 9.4857 8.7900 Ru 17.4295 7.0754 13.0141 79 H 17.8607 13.4567 4.9726 Ru 14.1782 14.6360 8.8062 80 H 12.5876 15.2278 18.4548 6 Ru 12.1222 13.4114 15.0643 73 H 9.5431 17.9815 11.9454 114 H 17.9076 11.7239 15.3486 134 H 20.8122 17.8216 17.1335 62 C 18.4766 14.7287 27.9907 138 O 21.9046 20.2454 19.2499 214 H 20.2450 24.5451 12.5801 257 H 21.5439 7.0413 15.3362 16 Ru 11.21038 13.44118 9.13531 92 C 20.28950 19.81206 12.75287 168 H 16.59689 15.28232 17.47915 242 H 22.22640 12.57268 16.64459 108 C 12.6188 18.9564 26.8861 184 O 23.7767 16.5535 19.2488 260 H 11.1432 4.6743 9.4734 336 H 30.1036 9.6769 23.6510 412 H 21.8972 24.4517 7.7623 419 H 13.1316 21.2743 17.0196 88 C 21.0977 3.3432 22.2044 164 H 16.2263 14.1771 22.1260 240 H 18.8048 8.8840 19.4047 289 H 9.7717 9.4847 16.6118 6 Ru 16.6218 16.8693 19.8497 82 C 7.5331 13.8285 17.1421 158 H 11.0905 19.4849 13.3488 222 H 15.5614 11.0334 5.7265 11.4929 76 C 10.2406 14.8533 151 H 15.8542 4.4859 15.9660 175 H 8.3603 9.9115 19.7602 61 C 13.2392 9.6069 7.1823 113 H 17.7293 13.2149 8.9897 7 Ru 13.7193 13.7148 13.248 83 C 16.0825 18.614 17.7388 H 14.2958 19.2338 12.2132 167 H 9.8268 12.3788 9.3311 H 16.7423 15.9644 9.2237 116 H 12.4086 9.8682 10.5625 61 H 10.4227 7.7226 8.6757 97 H 20.4736 8.8331 4.8253 37 Ru 14.9085 17.222 11.3305 113 O 15.4125 17.3428 8.1624 189 H 16.133 20.716 18.6576 198 H 13.4178 15.818 4.7718 91 O 9.5715 15.276 8.1344 142 H 16.633 18.5973 15.3761 7 Ru 13.6941 14.1801 13.7962 75 C 9.7473 8.3182 11.4948 15 Ru 13.3911 13.8073 8.8575 47 Ru 18.6572 9.4573 13.0969 Ru 18.9377 9.5012 4.6078 80 H 19.2262 12.7693 7.1400 Ru 13.9678 14.5482 17.4430 81 H 14.1248 17.7304 7.9402 7 Ru 13.6452 14.2466 12.9028 74 H 9.2551 13.7329 9.1307 115 H 7.6537 13.3914 14.7021 135 H 19.7173 19.1774 16.7664 63 C 19.2133 13.5667 28.6575 139 O 20.9087 21.1391 17.4347 215 H 20.0523 23.1483 10.4319 258 H 10.9817 19.3803 12.4016 17 Ru 9.84180 12.60581 11.24509 93 C 20.24413 20.69905 11.50758 169 H 18.18402 12.96049 14.13263 243 H 24.32108 11.29800 16.05251 109 C 12.9852 18.5706 25.4506 185 O 23.8670 15.1830 17.4486 261 H 13.3373 4.5078 11.6414 337 H 30.7025 10.1986 22.0630 413 H 21.7402 25.6323 9.9604 89 C 20.0778 4.3572 21.6853 165 H 20.1218 21.9040 14.6498 241 H 18.3026 9.2876 21.0499 290 H 11.4986 9.3307 14.7946 7 Ru 18.1153 17.6736 17.7116 83 C 8.8567 14.5796 16.9704 159 H 14.9636 25.7016 20.7767 223 H 14.4428 12.2374 7.6453 21.7065 77 C 10.7281 14.6903 152 H 17.0985 5.7104 15.5859 176 H 16.1492 14.7380 8.0933 62 C 7.9804 18.8931 16.6939 114 H 17.9874 11.1136 11.0093 8 Ru 12.4098 12.907 11.0627 84 O 6.6398 12.264 13.1659 H 17.4987 19.5283 7.3528 H 16.3153 12.6406 7.9036 117 H 10.8414 8.8691 14.8698 62 H 11.7746 13.3932 8.8590 98 H 20.4282 6.8887 6.0864 38 Ru 15.0273 17.3745 15.5579 114 O 15.9848 17.445 18.6872 190 H 17.5955 19.7238 18.8906 199 H 11.9638 14.8015 4.7869 92 O 7.873 10.9535 12.9007 143 H 20.1892 18.3565 13.7075 8 Ru 12.3495 13.3067 11.6872 76 O 6.5634 12.9832 13.6354 16 Ru 13.5385 9.3204 4.5935 48 Ru 18.7222 11.0226 6.7458 Ru 18.9807 9.5981 8.9092 81 H 17.3918 14.6984 9.9892 Ru 15.4180 17.0185 8.9084 82 H 13.9144 17.7367 18.3191 8 Ru 12.2229 13.4696 10.6811 75 H 10.3167 15.7640 16.8573 116 H 11.6471 19.7427 15.0128 136 H 20.4994 18.5341 14.5209 64 C 17.9823 15.9823 25.8427 140 O 23.7107 14.9466 18.1307 216 H 21.7564 22.7534 10.5732 259 H 12.0376 20.1325 11.2113 18 Ru 9.61867 12.72801 15.34424 94 C 19.09104 18.04049 14.13750 170 H 17.04743 8.91275 15.15830 244 H 23.75738 9.92865 17.00697 110 C 20.0938 18.9485 32.2261 186 O 14.4127 11.4134 15.7034 262 H 13.5051 5.3442 10.1005 338 H 30.6687 11.3437 23.4178 90 C 20.6385 5.7778 21.5752 166 H 16.6533 12.7666 17.6476 242 H 33.2714 13.5363 16.4365 291 H 10.6435 10.5637 13.8683 8 Ru 16.7664 16.8791 15.583 84 C 21.3826 2.4031 22.0676 160 H 13.9066 24.6453 21.6986 224 H 14.4837 10.7524 8.5932 20.2911 78 C 9.1068 9.1133 153 H 12.7926 10.4108 4.8120 177 H 16.4001 19.4418 7.0704 63 C 8.9151 18.2853 15.6864 115 H 19.4106 10.7839 12.5264 9 Ru 12.3728 11.2698 13.2114 85 O 7.751 10.2755 13.1206 H 16.4247 12.3320 18.2971 118 H 14.9850 14.9975 7.7682 63 H 10.5418 9.3756 7.0128 99 H 21.8632 6.5125 8.3664 39 Ru 13.9858 8.793 13.5348 115 O 15.3893 18.899 17.0664 191 H 16.2788 19.6068 20.0736 200 H 14.115 8.6443 11.7775 93 O 6.863 12.9565 13.201 144 H 19.1615 19.3185 12.5866 9 Ru 12.299 11.6991 13.7757 77 O 7.577 10.9458 13.6926 17 Ru 12.2167 8.5251 6.6046 49 Ru 18.7053 11.0031 10.9176 Ru 18.7515 9.3382 13.1327 82 H 16.3809 5.8345 4.8030 Ru 15.3981 17.0796 13.2118 83 H 15.2225 20.0017 12.1053 9 Ru 12.3023 11.9355 12.8346 76 H 11.8070 18.2384 9.0879 117 H 10.4950 12.4825 18.5687 137 H 20.4106 16.8040 14.9300 65 C 18.1134 16.1302 24.3398 141 O 23.6146 16.2813 19.9543 217 H 22.3253 25.2214 10.4432 260 H 12.3348 22.1220 12.7821 19 Ru 10.81844 13.50582 17.53990 95 C 17.86751 17.17220 14.34916 171 H 17.71613 14.67323 12.32227 245 H 25.38342 11.31083 18.32806 111 C 20.3349 19.0498 30.7192 187 O 14.1980 12.8114 13.9400 263 H 11.6265 6.8912 10.7313 339 H 28.1722 10.0907 22.0994 91 C 19.6238 6.7984 21.0528 167 H 20.0515 17.3674 12.4099 243 H 33.0981 14.9352 17.5158 292 H 11.0089 12.2182 15.7352 9 Ru 16.8172 15.2607 17.5986 85 C 20.4141 3.464 21.5428 161 H 23.0073 23.3541 18.1822 225 H 16.9978 10.7405 8.4708 19.6285 79 C 10.1173 9.5754 154 H 13.4799 8.8265 5.2205 178 H 16.0263 20.5745 8.4223 64 O 9.9236 18.9772 15.3051 116 H 18.4267 13.1324 16.7549 10 Ru 12.2238 15.923 13.2517 86 O 13.5525 13.375 19.6916 H 15.9001 18.8667 12.1828 119 H 15.2783 18.9689 14.0084 64 H 11.8685 8.9662 4.9635 100 H 20.5679 9.0633 12.5744 40 Ru 12.847 8.1677 15.6016 116 O 11.8845 19.3595 11.0315 94 O 15.6815 11.9875 19.3138 145 H 19.8738 17.7908 12.0357 Ru 12.1975 16.45 13.7578 78 O 13.6825 13.7986 20.2154 18 Ru 12.1264 8.6543 10.7720 50 Ru 18.7696 4.9135 8.6253 Ru 18.9071 11.0788 6.8020 83 H 15.1175 4.8987 7.6613 Ru 15.2137 16.8454 17.4862 84 H 15.6943 18.6868 9.3141 Ru 12.2349 16.5652 12.9940 77 H 11.9573 19.6110 11.9234 118 H 14.5350 14.9324 19.1263 138 H 18.2294 17.0612 13.9023 66 C 21.4288 23.1649 23.9889 142 O 20.1094 22.6593 14.3125 218 H 20.6093 25.5953 10.2986 261 H 11.2615 21.3511 13.9416 20 Ru 12.53715 15.82251 9.10774 96 C 8.40358 7.20986 18.32510 172 H 15.21566 9.20252 11.60342 246 H 24.35192 12.74286 18.13163 112 C 19.5583 18.0055 29.9131 188 O 15.3836 19.8595 23.0506 264 H 11.4512 6.0541 12.2714 340 H 28.1381 11.2244 23.4464 92 C 20.1880 8.2156 20.9308 168 H 20.7109 15.5400 13.9536 244 H 32.9179 13.2916 18.1591 293 H 11.8699 10.9851 16.6619 Ru 16.7034 19.9679 17.6677 86 C 21.0388 4.8587 21.4517 162 H 23.6568 22.1533 17.0813 226 H 16.9586 12.214 7.5028 18.6102 80 C 15.6835 19.7007 155 H 14.5813 10.1772 4.8517 179 H 14.7264 19.9424 7.3728 65 O 8.6765 17.0945 15.2818 117 H 18.0166 14.2684 14.1907 11 Ru 11.062 13.5338 13.1526 87 O 15.0113 11.6335 19.5572 H 15.2269 8.2517 13.1475 120 H 15.1284 14.6498 18.5753 65 H 10.4652 9.2438 10.4447 101 H 20.4647 10.1697 10.1560 41 Ru 15.0435 11.109 9.1926 117 O 13.1035 20.0505 12.8115 95 O 14.088 13.559 19.6487 146 H 9.5445 14.9625 15.7474 Ru 10.9858 14.047 13.7183 79 O 14.9402 11.9132 20.0323 19 Ru 13.5079 9.3459 12.9464 51 Ru 18.9020 6.4342 6.6804 Ru 18.7968 11.0506 11.0290 84 H 16.3452 4.5079 11.1949 Ru 15.2872 18.4979 11.0999 85 H 17.0863 18.0175 11.4334 Ru 10.9602 14.2234 12.8705 78 H 11.5599 18.0156 16.8404 119 H 11.8017 8.5358 14.5342 139 H 18.0678 18.7462 14.4904 67 C 22.2306 24.2998 24.6309 143 O 20.2765 21.4008 12.4453 219 H 21.6873 25.5730 8.0350 262 H 9.3940 21.4025 12.2425 21 Ru 11.02537 14.98290 11.25234 97 C 7.66788 6.26587 19.27944 173 H 13.11119 16.62393 7.82524 247 H 23.78159 11.36557 19.09269 113 C 19.7644 18.1144 28.4002 189 O 14.4793 17.7740 23.0587 265 H 13.7962 6.7109 12.9037 341 H 29.2227 12.9761 22.0025 93 C 19.1772 9.2271 20.3843 169 H 20.5856 16.9897 22.8157 245 H 31.0258 14.6083 16.1028 294 H 30.8882 25.1108 21.0503 Ru 15.379 17.5381 17.6339 87 C 20.0816 5.9262 20.916 163 H 21.2034 9.7139 19.3392 227 H 15.8127 13.4225 9.4086 7.8588 81 C 15.4706 18.5267 156 H 18.0163 14.4909 11.5810 180 H 11.0660 8.2460 15.5683 66 O 14.408 10.0271 7.5023 118 H 19.0528 11.6454 14.061 12 Ru 8.404 13.3348 13.0528 88 O 17.891 13.6188 8.0067 H 16.3211 10.6884 9.2258 121 H 16.6892 17.5095 10.9772 66 H 12.1958 11.8019 6.4599 102 H 21.5061 7.5599 10.0023 42 Ru 13.727 10.3152 11.3261 118 O 12.8073 15.8563 7.2618 96 O 20.0895 12.973 15.3239 147 H 14.7983 8.5363 5.5604 Ru 8.3795 13.9776 13.6254 80 O 17.8583 13.898 8.4678 20 Ru 14.7315 11.6540 4.6166 52 Ru 20.1749 7.1268 8.8402 Ru 18.8131 4.8630 8.7820 85 H 16.0897 6.3722 14.0675 Ru 15.2099 18.4195 15.3233 86 H 15.2302 19.9184 14.3268 Ru 8.2112 14.2670 12.7048 79 H 10.9700 12.7017 7.7010 120 H 16.2108 13.1814 8.5521 140 H 15.7899 9.7188 7.6479 68 C 22.5881 24.0183 26.0909 144 O 23.3553 16.7878 14.0580 220 H 22.2254 23.8992 8.2862 263 H 10.4734 22.1726 11.0814 22 Ru 10.95796 14.96986 15.39288 98 C 6.33813 5.76743 18.71202 174 H 10.37517 15.21041 17.15261 248 H 19.96562 17.37064 14.11738 114 C 19.0125 17.0431 27.6070 190 O 14.1354 13.2239 20.5584 266 H 13.9869 7.5337 11.3554 342 H 29.2570 11.8431 20.6527 94 C 32.7037 13.9328 17.2908 170 H 20.6748 20.4299 21.9258 246 H 30.8406 12.9763 16.7378 295 H 30.4927 25.1314 19.3194 Ru 12.8125 17.6344 17.5309 88 C 20.7193 7.3115 20.7806 164 H 20.8495 10.0622 21.0481 228 H 15.8851 11.9588 10.3766 8.7813 82 C 15.9805 19.7133 157 H 13.5908 16.8453 9.9987 181 H 15.4914 20.6233 18.7355 67 O 12.1424 10.0919 7.6236 119 H 18.0139 11.1584 15.8903 13 Ru 9.4645 15.5403 13.2699 89 O 19.1878 12.8515 9.6977 H 16.7803 9.2719 11.2992 122 H 12.3280 8.2912 12.5566 67 H 13.1054 11.0725 12.6901 103 H 20.2704 7.0276 11.7941 43 Ru 13.8598 10.3295 15.7524 119 O 13.34 13.65 7.1477 97 O 20.1695 11.653 13.4662 148 H 13.9928 9.7883 4.582 Ru 9.527 16.1781 13.7726 81 O 19.1622 13.392 10.2553 21 Ru 13.4757 10.9015 6.7116 53 Ru 18.8297 6.3894 10.9196 Ru 19.0518 6.3950 6.6249 86 H 17.7236 10.2368 3.4532 Ru 14.1586 9.9558 13.3167 87 H 14.2502 11.0645 9.1568 Ru 9.5232 16.4440 12.9371 80 H 10.0665 9.5073 11.3000 121 H 16.5196 16.4328 9.9647 141 H 14.1175 9.4705 7.0539 69 C 21.0630 23.4506 22.5332 145 O 22.1879 17.4142 12.2208 221 H 20.4951 24.2614 8.1474 264 H 9.0320 23.8892 12.2057 23 Ru 12.16326 15.82959 17.61807 99 C 9.74738 7.68083 18.88921 175 H 12.21767 17.49561 9.46010 249 H 19.20606 18.64718 15.05309 115 C 19.1672 17.1813 26.0906 191 O 15.4305 13.9705 22.2560 267 H 12.0852 9.0733 11.9330 343 H 26.7447 11.7007 20.7026 95 C 31.2039 13.9856 16.9963 171 H 22.2852 18.1220 18.2282 247 H 30.5232 13.8950 19.0487 296 H 29.8120 26.3638 20.3998 Ru 13.9636 19.7351 17.6854 89 C 19.7442 8.371 20.2622 165 H 18.4226 11.9963 10.2344 229 H 33.3953 19.165 12.8459 19.0982 83 C 15.5772 18.5304 158 H 10.6160 15.2176 17.3808 182 H 17.0693 19.8483 19.0186 68 O 18.481 16.4409 15.463 120 H 9.177 11.2888 11.7004 14 Ru 9.7513 10.9955 13.1786 90 O 9.1467 15.7925 10.0682 H 18.1836 10.0531 13.2563 123 H 14.3434 10.1127 17.0009 68 H 14.4450 13.2698 12.6859 104 H 11.7550 6.7674 6.9545 44 Ru 15.1877 11.301 17.8459 120 H 9.1373 17.2535 13.4537 98 O 10.9883 7.89 11.6935 149 H 12.9973 8.6455 5.505 Ru 9.5685 11.5952 13.8079 82 O 9.1182 16.2267 10.5185 22 Ru 13.4148 10.8331 10.8450 54 Ru 20.0690 8.7559 6.7154 Ru 20.3569 7.0637 8.8130 87 H 18.7398 7.8621 14.0853 Ru 12.5967 9.4649 15.5622 88 H 12.9830 9.8563 11.9988 Ru 9.3438 11.7195 12.7879 81 H 11.1101 10.6435 9.1110 122 H 16.2948 16.0531 17.7880 142 H 15.2541 9.1132 4.9465 70 C 20.2238 22.3857 21.8616 146 O 15.2034 22.9898 20.3465 222 H 26.2647 15.3798 18.5894 265 H 9.6408 23.3840 13.7968 24 Ru 12.27303 17.33061 11.31270 100 C 10.46381 8.70682 18.03486 176 H 13.44049 16.79067 18.43112 250 H 18.14491 19.57183 12.94558 116 C 14.2684 31.9253 22.7614 192 O 19.7857 22.8144 20.0637 268 H 11.8842 8.2534 13.4803 344 H 26.7048 12.8207 22.0630 96 C 30.3776 14.5369 18.1616 172 H 21.2681 14.0354 19.4688 248 H 30.7688 15.5313 18.4421 297 H 29.1802 23.3436 20.5430 Ru 13.9157 15.1736 17.6746 90 C 13.5968 9.3604 4.7027 166 H 18.3456 13.4526 9.2653 230 H 32.5353 18.6249 11.3893 18.2532 84 C 12.6087 21.5480 159 H 11.2666 16.9695 9.9745 183 H 15.7384 19.5341 20.1523 69 O 17.3534 18.3928 15.7903 121 H 9.4338 11.1433 15.2639 15 Ru 10.5578 17.868 13.0884 91 O 9.5558 14.683 8.1377 H 16.4267 10.5349 17.0289 124 H 13.3118 7.8944 14.2741 69 H 13.3628 14.1726 7.1075 105 H 11.5614 6.8561 10.5018 45 Ru 16.3188 13.4165 9.2032 121 H 11.1995 14.7785 8.5909 99 O 10.9395 9.252 9.8813 150 H 13.6893 18.3557 16.1359 Ru 10.6712 18.4826 13.6587 83 O 9.464 14.9693 8.6646 23 Ru 14.7018 11.6363 12.9271 55 Ru 20.0796 8.7412 10.8796 Ru 18.9326 6.3997 10.9691 88 H 20.5929 10.5889 7.0980 Ru 15.5024 12.4461 8.8794 89 H 14.2588 9.7322 15.4449 Ru 10.8212 18.6638 13.0170 82 H 9.2635 9.8963 13.3870 123 H 17.5769 13.8717 17.6047 143 H 16.6426 10.1046 5.4447 71 C 12.8111 25.7447 19.6024 147 O 14.0921 23.5398 18.4539 223 H 25.6919 13.9905 19.4855 266 H 10.7344 24.1576 12.6343 25 Ru 13.53097 18.11340 13.45936 101 C 15.68690 4.32082 13.08507 177 H 9.13701 13.17039 17.01085 251 H 18.92125 18.30868 12.00271 117 C 14.9997 30.7951 22.0351 193 O 20.0257 21.5174 21.9051 269 H 14.1889 8.9672 14.1779 345 H 27.7808 14.5955 20.6363 97 C 28.8831 14.6556 17.8517 173 H 9.2914 14.7826 18.8604 249 H 28.7515 15.2887 16.9567 298 H 28.5061 24.5658 21.6162 Ru 15.1603 21.9933 17.6188 91 C 13.5993 10.1685 6.0005 167 H 22.0724 18.7096 16.5121 231 H 32.3589 20.2976 11.9538 11.2224 85 C 12.6827 20.1127 11.6719 86 C 12.9972 14.7404 160 H 13.6908 16.0865 18.8449 161 H 9.4414 12.4609 17.4409 184 H 10.3611 11.4246 9.9541 185 H 13.3908 22.1437 11.7043 70 O 12.5631 9.4127 18.8143 71 O 12.8404 7.6885 17.353 122 H 9.8018 12.8939 17.397 123 H 10.4428 15.7867 9.6813 16 Ru 11.1088 13.5403 8.9523 17 Ru 9.806 12.625 11.1332 92 O 10.895 19.08 16.0176 93 O 9.9218 19.5935 14.0387 100 H 16.5378 9.1338 14.9000 101 H 17.9472 13.6215 9.1850 125 H 13.8087 12.1679 18.5471 126 H 16.8798 15.7114 17.1184 70 H 14.4437 13.3093 4.9227 71 H 14.7820 15.1787 8.6766 106 H 11.8233 8.9542 12.5737 107 H 13.1078 11.1455 4.9628 46 Ru 16.3993 13.501 13.487 47 Ru 16.4723 13.5843 17.7104 122 H 8.308 13.2075 11.2752 123 H 9.703 11.1198 16.5334 100 O 11.2323 16.8525 19.0663 101 O 10.0563 14.9065 18.9719 151 H 8.0252 19.51 16.7495 152 H 7.3005 18.2435 15.703 Ru 10.9731 13.8664 9.5606 Ru 9.7767 13.1155 11.7065 84 O 10.9944 19.5299 16.6793 85 O 9.939 20.0896 14.7552 24 Ru 14.7253 13.2019 6.8248 56 H 11.6729 13.3685 8.8501 Ru 20.2537 8.8291 6.8125 89 H 19.1870 12.7824 10.9821 Ru 14.2921 11.4866 11.0293 90 H 14.0265 11.6352 18.4282 Ru 10.9127 14.2068 8.6713 83 H 11.6787 9.8346 17.1740 124 H 9.8080 6.9272 15.0100 144 H 15.4593 11.6616 3.9811 72 C 12.3244 26.9957 20.3376 148 O 19.8271 22.6347 20.6581 224 H 25.6311 15.4035 21.6094 267 H 17.1165 14.6973 8.5816 26 Ru 12.15346 17.35756 15.63556 102 C 16.14070 2.85900 13.07467 178 H 18.29762 11.09632 11.67446 252 H 21.18795 19.17218 12.71833 118 C 14.1311 29.5500 21.8402 194 O 19.9277 22.7278 13.7230 270 H 14.4256 9.7531 12.6107 346 H 27.8188 13.4768 19.2726 98 C 28.0571 15.2397 19.0012 174 H 8.5684 16.4143 18.9590 250 H 28.4827 13.6630 17.5802 299 H 27.4047 25.6876 19.6513 Ru 15.378 17.3831 13.4874 92 C 15.0073 10.487 6.5106 168 H 19.0999 13.0242 16.2626 232 H 31.3831 17.7982 13.4842 Domain 1 -Ru 55 25 Ru 16.1772 14.0626 8.8744 57 H 13.3022 10.8858 3.7628 Ru 20.1345 8.6764 10.9676 90 H 17.6713 3.5651 9.1055 Ru 14.1110 11.5797 15.2115 91 H 15.5899 15.4767 7.7882 Ru 9.6464 13.3210 10.8343 84 H 12.2183 15.0116 7.5743 125 H 10.8832 5.9402 16.0550 145 H 13.8708 11.1145 4.5729 73 C 11.2000 27.7137 19.5893 149 O 19.9484 21.3220 22.4990 225 H 26.2743 16.7644 20.7031 268 H 17.0536 13.0360 9.1314 27 Ru 11.13010 8.83659 13.35114 103 C 16.69682 2.42597 11.71718 179 H 9.66655 9.42463 14.18655 253 H 20.40140 20.44315 13.65139 119 C 14.8362 28.4051 21.1089 195 O 20.0082 21.5163 11.8191 271 H 12.8737 12.2969 1.7309 347 H 25.3079 13.3184 19.3258 99 C 26.5906 15.4753 18.6300 175 H 18.1010 15.7150 26.4769 251 H 28.1169 14.5691 19.8770 300 H 28.0798 24.4654 18.5749 Ru 14.1785 16.6583 15.575 93 C 15.0178 11.3078 7.8019 169 H 18.0684 20.6637 12.4427 233 H 31.2144 19.4555 14.0551 5.1435 87 C 13.0747 14.6535 162 H 18.1629 10.9115 11.6070 186 H 11.6270 21.9585 11.5012 72 H 6.6571 13.6796 13.6475 124 H 12.0577 14.8209 8.0548 18 Ru 9.6505 12.6278 15.1325 94 O 16.9605 16.9773 12.7436 102 H 17.9736 11.6721 10.4033 127 H 18.1133 15.1175 11.0810 72 H 13.5006 14.2531 10.5709 108 H 14.8415 10.1362 3.4429 48 Ru 16.2862 15.0397 11.2343 124 H 15.0793 18.376 12.622 102 O 11.4768 10.306 18.4083 153 H 7.4393 19.898 15.0943 Ru 9.6128 13.2659 15.752 86 O 16.7621 17.8651 13.6038 26 Ru 14.6851 13.1189 10.8784 58 H 10.7433 7.7890 7.6769 H 9.3149 9.4925 8.5644 91 H 19.0459 6.1082 4.8619 Ru 15.3367 12.2928 17.3297 92 H 16.6190 13.1196 18.4263 Ru 9.5316 13.3190 14.7867 85 H 12.0074 14.7051 18.2755 126 H 8.7750 4.9264 16.6835 146 H 14.2283 13.0678 6.0112 74 C 13.9267 25.0110 20.3461 150 O 17.4840 17.1046 23.8081 226 H 28.3235 15.4011 20.1194 269 H 19.6053 12.9522 9.1116 28 Ru 12.53203 11.36571 9.07064 104 C 15.15056 4.76825 14.45119 180 H 17.87176 13.10625 17.49061 254 H 21.14492 21.32297 11.42107 120 C 13.9493 27.1703 20.9338 196 H 9.3134 13.5362 17.0854 272 H 14.6489 12.2625 1.7027 348 H 25.2645 14.4289 20.7007 100 C 13.3182 10.2771 4.9198 176 H 16.7398 16.8602 26.4557 252 H 28.5089 16.1959 19.3212 301 H 26.8296 22.6713 19.8212 Ru 14.0448 16.8189 19.7345 94 C 16.4206 11.6662 8.2969 170 H 14.867 19.2945 21.5442 234 H 29.7791 20.0036 12.0697 6.6457 88 O 6.6999 12.2333 13.4274 89 O 7.7284 10.2073 13.2187 90 O 14.0569 13.1839 19.9917 91 O 16.1618 12.3961 19.6577 92 O 17.9685 12.7862 8.1988 93 O 19.3183 12.5435 9.9983 94 O 9.0594 15.3245 10.6477 95 O 8.9698 13.7976 8.9750 96 O 11.0669 18.4453 16.6990 97 O 10.1182 19.1824 14.7792 98 O 16.8739 18.0242 15.1641 99 O 18.0656 16.1022 15.1914 100 O 14.1723 6.3551 15.6989 101 O 15.2953 6.9317 13.8302 102 O 14.7721 10.3756 7.3673 103 O 12.5108 10.4155 7.3745 104 O 19.8164 11.9233 15.8173 105 O 19.8152 10.6743 13.9215 106 O 10.0171 7.3616 12.6493 107 O 9.7678 8.6837 10.8355 108 O 11.4243 15.6408 19.7906 109 O 10.4275 13.6051 19.6806 110 O 9.8809 9.3819 17.3808 111 O 11.1663 10.1718 19.0654 112 O 15.3406 18.7439 10.0241 113 O 15.4232 17.3640 8.2188 114 O 15.7273 17.3663 18.7738 115 O 15.1290 18.7477 17.0833 116 O 12.0978 19.2310 10.9603 117 O 13.3070 19.8710 12.7655 118 O 12.7741 15.7162 7.3051 119 O 13.4179 13.5416 7.1690 120 H 9.1603 17.0559 13.3454 121 H 11.0641 14.7065 8.6603 122 H 9.1584 10.7394 15.3474 123 H 15.2456 18.1077 12.7759 124 H 13.1294 18.6416 15.1514 125 H 12.4909 9.1653 10.6846 126 H 13.9270 10.2764 18.8648 127 H 16.6591 16.7406 11.5287 128 H 16.6057 10.0688 9.6585 129 H 16.8319 15.2371 17.4272 130 H 18.2314 12.8321 13.9985 131 H 17.2474 8.7958 15.0903 132 H 5.4227 9.2142 13.1725 133 H 4.9582 10.5547 12.0836 134 H 4.6391 10.7007 13.8189 135 H 16.2686 12.0420 22.1359 136 H 14.5622 11.4977 22.0872 137 H 14.9222 13.1877 22.4790 138 H 21.1253 11.9351 8.3268 139 H 20.6263 13.4298 7.4893 140 H 19.9984 11.8713 6.9207 141 H 6.8064 14.8567 8.2957 142 H 7.3153 16.4455 8.9642 143 H 6.4532 15.2995 10.0001 144 H 8.8589 20.8073 16.2781 Roberto González Gómez 399 163 H 22.3120 10.5058 14.2589 164 H 21.8789 9.9800 15.9069 165 H 22.3598 11.6670 15.6394 166 H 8.3480 6.8430 9.8648 167 H 7.6150 6.6590 11.4867 168 H 8.9631 5.6082 11.0230 187 H 12.6967 21.6023 10.1309 188 H 16.3403 9.7011 17.2204 189 H 13.5568 13.9227 4.6780 190 H 13.3778 15.7112 4.8045 191 H 11.9420 14.6718 4.8393 192 H 15.2271 9.0320 11.1949 Domain 19 -Ru 55 (CH 3 COO) 4 (H) 74 1 Ru 15.3816 12.8156 15.2482 2 Ru 15.0911 13.0185 10.9542 3 Ru 15.1038 11.3416 13.0558 4 Ru 14.0368 15.1687 15.5358 5 Ru 13.6758 15.4231 11.1776 6 Ru 12.5574 12.8414 15.496 7 Ru 13.868 13.7448 13.2628 8 Ru 12.2459 13.0889 11.1838 9 Ru 12.4184 11.4604 13.2266 10 Ru 12.4808 16.1026 13.5234 11 Ru 11.083 13.8157 13.47 12 Ru 8.2563 13.7225 13.7127 13 Ru 9.7988 16.1917 13.7634 14 Ru 9.6468 11.3814 13.44 15 Ru 11.2536 18.3087 13.8466 16 Ru 10.8553 13.9843 9.2526 17 Ru 9.6503 13.1513 11.4411 18 Ru 9.9212 12.9192 15.6064 19 Ru 11.4664 13.4431 17.6994 20 Ru 12.2448 16.2245 9.2128 21 Ru 10.9909 15.4701 11.4307 22 Ru 11.306 15.1957 15.694 23 Ru 12.838 15.6877 17.7397 24 Ru 12.3852 17.7578 11.478 25 Ru 13.9042 18.4863 13.5562 26 Ru 12.8188 17.4787 15.7937 27 Ru 10.9982 9.078 13.2219 28 Ru 12.0539 11.7244 8.9415 29 Ru 10.9334 10.7973 11.2101 30 Ru 11.2163 10.5713 15.365 31 Ru 12.6268 11.1122 17.5314 32 Ru 13.4935 13.942 9.0003 33 Ru 14.0972 13.3645 17.5882 34 Ru 14.8427 16.17 9.0247 35 Ru 15.1556 16.0584 13.2908 36 Ru 15.4551 15.642 17.6056 37 Ru 15.1384 17.7249 11.1905 38 Ru 15.464 17.4499 15.6414 39 Ru 13.6669 9.0244 13.1242 40 Ru 12.5747 8.4208 15.4899 41 Ru 14.7841 11.6751 8.7142 42 Ru 13.5853 10.7478 10.9645 43 Ru 13.878 10.5105 15.2121 44 Ru 15.3195 11.0377 17.3883 45 Ru 16.1341 13.8658 8.7984 46 Ru 16.5521 13.6843 13.0782 47 Ru 16.7098 13.3565 17.3351 48 Ru 16.419 15.3805 11.0146 49 Ru 16.76 15.1374 15.3642 50 Ru 16.2605 9.0893 12.9139 51 Ru 16.2289 10.6158 10.8097 52 Ru 17.9196 11.2527 12.8626 53 Ru 16.5669 10.4382 15.073 54 Ru 17.6118 13.0004 10.8091 Roberto González Gómez 400 73 H 13.7106 20.0291 12.8458 74 H 10.3289 7.6175 13.1166 75 H 15.9368 19.0773 10.869 76 H 8.07 15.3599 13.382 77 H 7.9388 12.0181 13.4305 78 H 9.7511 17.8643 13.0858 79 H 8.0004 13.7712 11.9731 80 H 9.2162 13.5253 9.7331 81 H 8.0463 13.1783 15.3146 82 H 9.4241 15.7941 12.0924 83 H 11.0287 15.3211 17.5437 84 H 12.3876 17.4006 17.5115 85 H 10.7663 17.2915 11.2062 86 H 12.1673 17.9586 9.725 87 H 11.5217 19.1194 12.3113 88 H 12.7113 19.1029 14.7493 89 H 9.3147 9.581 13.4674 90 H 10.4304 8.9859 11.6236 91 H 10.5503 11.0259 9.4388 92 H 11.4515 11.9394 18.6264 93 H 11.0813 10.4228 17.1486 94 H 13.5038 17.0319 8.2172 95 H 14.2511 16.3886 18.6656 96 H 15.2574 17.8962 9.4833 97 H 14.1888 20.174 13.6139 98 H 15.7731 17.3481 17.3978 99 H 13.3696 12.4317 7.8288 100 H 13.6104 9.056 11.3439 101 H 14.8597 9.7611 10.1363 102 H 15.4734 10.0141 18.6066 103 H 16.6749 15.6866 9.2658 104 H 16.0102 12.5565 7.6446 105 H 16.7416 11.7378 18.179 106 H 15.4659 18.6115 12.6423 125 H 12.8423 14.0902 18.781 126 H 13.7581 18.7743 10.8643 127 H 10.7557 12.6107 8.0864 128 H 12.1703 9.8648 10.3239 129 H 10.8678 8.6083 14.959 130 H 14.7982 14.7769 7.842 131 H 15.1745 18.9426 14.6798 132 H 15.5372 14.1001 18.6088 133 H 16.8064 17.1878 11.1944 134 H 12.2264 8.0647 12.5378 135 H 14.4061 9.6935 16.9333 136 H 13.3061 7.59 14.1926 137 H 14.1434 11.7128 18.571 138 H 17.2238 15.1091 17.1867 139 H 18.0938 14.7087 10.9511 140 H 16.8898 15.5172 12.7288 141 H 18.6513 12.7501 12.2475 142 H 12.0072 6.4028 19.5014 143 H 12.5472 7.6956 20.6318 144 H 13.7357 6.7224 19.7058 145 H 16.4039 16.8801 14.2461 146 H 19.5915 19.5107 15.6274 147 H 20.4647 18.0298 15.0816 148 H 20.1304 18.2834 16.8056 149 H 7.4388 14.6988 14.672 150 H 12.136 8.2825 5.8962 151 H 13.5429 7.5466 6.7236 152 H 13.8178 8.6413 5.3595 153 H 14.1788 18.32 16.546 154 H 6.9798 18.458 16.5987 155 H 7.9472 19.9818 16.5757 156 H 8.3589 18.6709 17.703 157 H 9.6252 14.6311 15.8642 Domain 37 -Roberto González Gómez 401 19 Ru 10.7648 13.4463 17.3181 20 Ru 12.367 15.9813 9.0293 21 Ru 10.8808 15.0673 11.0885 22 Ru 10.8043 14.955 15.2552 23 Ru 11.975 15.9035 17.4814 24 Ru 12.1438 17.425 11.1894 25 Ru 13.3988 18.2838 13.4186 26 Ru 11.8643 17.3833 15.3286 27 Ru 11.373 8.9165 13.1651 28 Ru 12.6063 11.3703 9.0067 29 Ru 11.2095 10.5363 11.0391 30 Ru 11.1648 10.3303 15.2849 31 Ru 12.3815 11.2328 17.4164 32 Ru 13.7715 13.7335 9.0262 33 Ru 13.4603 13.664 17.5167 34 Ru 14.946 16.102 9.0587 35 Ru 14.82 16.1663 13.2925 36 Ru 14.5965 16.0453 17.5794 37 Ru 14.5693 17.7533 11.1974 38 Ru 14.432 17.6183 15.4651 39 Ru 14.0253 9.2123 13.136 40 Ru 12.99 8.2065 15.0834 41 Ru 15.1553 11.4288 9.1463 42 Ru 13.8533 10.7112 11.1264 43 Ru 13.7323 10.5433 15.3626 44 Ru 14.8803 11.4753 17.4866 45 Ru 16.2818 14.1153 9.1471 46 Ru 16.4525 13.7578 13.3718 47 Ru 16.029 14.0003 17.5097 48 Ru 16.3478 15.3663 11.2975 49 Ru 16.161 15.3685 15.4799 50 Ru 16.4525 9.2263 13.6513 51 Ru 16.4545 10.7165 11.363 52 Ru 17.7762 11.4938 13.3908 53 Ru 16.3825 10.8503 15.4976 54 Ru 17.7155 13.173 11.2141 55 Ru 17.5668 13.0465 15.5938 56 C 5.361 10.2542 13.2012 57 C 6.6843 10.9743 13.1628 58 C 14.2638 12.3218 21.7155 59 C 14.2733 12.4685 20.2155 60 C 20.1485 13.0382 7.5096 61 C 19.008 13.1715 8.4835 62 C 7.6403 16.1118 8.249 63 C 8.868 15.4875 8.8595 64 C 9.6395 21.1063 15.8681 65 C 10.1813 19.8373 15.2677 66 C 19.1333 17.7848 13.3455 67 C 17.851 17.0758 13.6729 68 C 16.2443 5.2333 15.4955 69 C 15.66 6.5487 15.0467 70 C 14.0843 9.696 5.2666 71 C 14.0008 10.3013 6.6407 72 C 21.7993 12.1255 15.0316 73 C 20.3125 12.1978 14.8096 74 C 9.3283 6.7 10.0248 75 C 10.114 7.765 10.7401 76 C 9.0045 9.003 18.9498 95 O 17.6865 16.6148 14.8489 96 O 14.4695 6.8283 15.4266 97 O 16.4115 7.2858 14.3159 98 O 15.0933 10.5938 7.2384 99 O 12.838 10.468 7.1625 100 O 19.6318 12.946 15.6016 101 O 19.8018 11.501 13.8692 102 O 10.478 7.5233 11.9486 103 O 10.359 8.8558 10.1265 104 O 9.7543 9.5823 16.7487 105 O 11.0135 10.2123 18.5193 106 O 10.2195 13.8078 19.3151 107 O 11.1688 15.8723 19.3911 108 O 15.8825 18.97 10.159 109 O 16.1363 17.66 8.3322 110 O 15.86 17.534 18.3747 111 O 15.6533 18.8483 16.5461 112 H 5.5083 9.1725 13.2683 113 H 4.7898 10.4955 12.2936 114 H 4.7732 10.6102 14.0582 115 H 15.2363 11.9643 22.0722 116 H 13.5078 11.5693 21.9869 117 H 13.9962 13.27 22.1941 118 H 20.988 12.5093 7.9716 119 H 20.4753 14.04 7.1955 120 H 19.8115 12.5078 6.6097 121 H 7.611 15.9333 7.1692 122 H 7.6245 17.188 8.462 123 H 6.7468 15.6703 8.7131 124 H 8.7425 21.4338 15.3322 125 H 10.404 21.8933 15.7786 126 H 9.4275 20.9628 16.9335 127 H 19.7447 17.9203 14.2433 128 H 18.9105 18.7545 12.8814 129 H 19.6893 17.1863 12.6084 130 H 16.6418 4.6918 14.6268 131 H 15.493 4.626 16.0098 132 H 17.0893 5.4248 16.1723 133 H 13.1288 9.7962 4.7414 134 H 14.3218 8.626 5.3635 135 H 14.8933 10.1653 4.694 136 H 18.0558 14.906 10.9452 137 H 16.159 9.992 9.7609 138 H 13.577 16.7533 8.0005 139 H 10.2535 15.2045 17.0269 140 H 11.5325 17.5258 9.5295 141 H 13.234 16.8925 18.3232 142 H 9.2825 12.547 16.9216 143 H 18.2225 11.368 11.6173 144 H 22.2983 11.68 14.1653 145 H 21.9987 11.5058 15.9185 146 H 22.1983 13.127 15.235 147 H 17.7563 13.545 17.3329 148 H 9.3618 6.8563 8.9419 149 H 8.2805 6.7593 10.3568 150 H 9.7043 5.7045 10.2885 151 H 8.9005 17.289 12.9665 152 H 8.77 9.6983 19.766 Roberto González Gómez 402 Domain 3 -Ru 55 (H) 35 Ru 17.5082 8.6051 10.9313 Ru 17.6177 8.5722 6.6214 Ru 17.5507 7.0962 8.7546 Ru 16.0901 10.9369 10.9886 Ru 16.1601 10.9894 6.6099 Ru 14.8500 8.5636 10.8940 Ru 16.2496 9.4378 8.7521 Ru 14.8584 8.5829 6.6027 Ru 14.8613 7.0074 8.7478 Ru 14.9037 11.7145 8.7762 Ru 13.4647 9.2969 8.7589 Ru 10.9211 9.4800 8.5794 Ru 12.2012 11.6624 8.7685 Ru 12.0712 7.0034 8.6022 Ru 13.3589 13.7202 8.8338 Ru 13.5668 9.3035 4.5435 Ru 12.2282 8.5407 6.5920 Ru 12.1007 8.6077 10.7625 Ru 13.4046 9.1473 12.8676 Ru 14.9009 11.5859 4.5411 Ru 13.5201 10.9241 6.7176 Ru 13.4467 10.8751 10.8183 Ru 14.6933 11.5206 12.9682 Ru 14.8349 13.1943 6.6878 Ru 16.1388 14.1057 8.8219 Ru 14.7171 13.1891 10.9477 Ru 13.6291 4.8044 8.7983 Ru 14.9832 7.1464 4.5359 Ru 13.6031 6.3327 6.6056 Ru 13.3180 6.4171 10.7155 Ru 14.7761 6.9685 12.8876 Ru 16.2288 9.4092 4.5623 Ru 16.0694 9.2918 13.0921 Ru 17.4677 11.6251 4.5577 Ru 17.5209 11.8236 8.8460 Ru 17.3666 11.5828 13.1651 Ru 17.4929 13.1849 6.7152 Ru 17.3729 13.1717 10.9725 Ru 16.3275 4.7576 8.9945 Ru 14.7788 4.5779 11.3203 Ru 17.4881 7.1924 4.5574 Ru 16.2559 6.2327 6.6774 Ru 16.3212 6.3032 10.8955 Ru 17.5305 7.0854 12.9700 45 Ru 18.7623 9.4098 4.5541 46 Ru 18.9550 9.4242 8.8473 47 Ru 18.6982 9.4050 13.0934 48 Ru 18.8425 10.9325 6.7182 49 Ru 18.6958 10.9471 11.0099 50 Ru 18.7293 4.8506 8.8260 51 Ru 18.9012 6.3300 6.7703 52 Ru 20.4161 7.1466 8.8873 53 Ru 18.8715 6.3865 10.8821 54 Ru 20.1545 8.6723 6.7552 55 Ru 20.0771 8.6456 11.0456 56 H 10.4736 11.1977 8.8682 57 H 13.3844 14.3709 10.4684 58 H 14.4082 13.2590 12.7478 59 H 13.3038 7.6089 13.7620 60 H 10.7039 7.8635 7.6772 61 H 10.4205 8.7101 10.1144 62 H 11.8725 8.8187 4.8421 63 H 13.1051 11.1202 4.8652 64 H 12.9278 10.9891 12.6588 65 H 14.5801 14.7026 7.7667 66 H 17.0172 14.7807 7.4522 67 H 15.8172 14.5958 10.5174 68 H 12.3902 5.2446 7.5783 69 H 13.8018 7.9466 3.4039 70 H 14.7102 5.4214 5.5564 71 H 12.3303 4.9808 9.9062 72 H 16.1850 12.4255 3.5616 73 H 15.9962 10.8270 14.2175 74 H 16.0466 7.6929 14.0830 75 H 17.6255 14.4647 9.6382 76 H 18.6368 10.8267 14.2093 77 H 18.8484 12.5148 5.6535 78 H 18.6864 12.5830 12.0885 79 H 14.5716 5.1156 13.0267 80 H 14.8683 3.6393 9.7112 81 H 18.8664 7.8923 3.5607 82 H 17.7137 5.4612 5.7129 83 H 18.8717 5.9780 12.6593 84 H 19.3772 11.2216 9.3659 85 H 20.3601 10.1760 5.8180 86 H 20.4756 9.1166 12.7042 87 H 21.2816 8.5087 8.1912 88 H 20.2509 5.5278 9.8017 Roberto González Gómez 403 103 H 19.4043 11.3175 12.6287 104 H 18.1239 13.6642 16.9661 105 H 18.0350 14.9226 14.6569 128 H 16.9307 15.9597 12.6824 129 H 18.7679 13.1071 12.3942 130 H 12.0058 6.8197 19.6021 73 H 11.7690 5.1898 9.0032 74 H 13.0375 4.5559 7.3483 75 H 13.4648 6.0837 4.9312 109 H 14.8358 10.0109 14.1458 110 H 16.3195 14.5903 6.9952 111 H 13.5878 7.8460 3.5859 49 Ru 16.4435 15.116 15.5399 50 Ru 16.4165 8.9545 13.5551 51 Ru 16.4275 10.3975 11.3589 125 H 14.5003 18.9125 14.7516 126 H 12.3462 9.373 10.7645 127 H 11.178 11.9925 18.7387 103 O 10.0473 9.9618 16.692 104 H 8.1548 15.799 13.039 105 H 11.3303 19.8085 13.6484 154 H 9.6163 13.2733 17.0404 155 H 21.698 13.57 8.3907 156 H 20.9158 14.7058 7.2327 Ru 10.8443 14.0759 17.8889 Ru 12.2904 16.3391 9.5262 Ru 10.8265 15.5147 11.5934 87 O 17.7493 17.0597 15.4624 88 O 13.8008 7.1618 15.9639 89 O 15.144 7.8408 14.278 1 Ru 11.0177 9.5196 8.7214 2 Ru 12.3433 11.7107 8.7628 29 Ru 17.4431 11.6471 4.4877 30 Ru 16.2502 10.9666 27 Ru 13.6550 4.8038 8.8877 28 Ru 14.9219 7.1083 4.6336 59 H 11.6473 6.6719 10.4698 60 H 16.1092 14.6353 7.1443 H 12.6919 3.4571 9.3736 H 10.4803 11.1240 8.8598 92 H 17.8277 5.0712 6.7574 93 H 20.5475 5.3525 8.4227 Ru 16.8021 14.7450 8.9461 Ru 16.8393 14.8344 13.2424 93 H 18.4511 15.8539 11.3936 94 H 17.0271 18.0276 15.3160 Ru 10.7590 13.9589 17.0772 Ru 12.2227 16.5687 8.7270 86 H 13.5825 17.3687 7.7859 87 H 13.3910 17.1538 18.2068 Domain 52 -Ru 55 (THF) 3 (H) 53 127 H 7.8721 6.4253 16.3643 128 H 8.0919 6.4886 18.8078 147 H 15.9836 12.7268 6.1318 75 C 14.4370 23.7623 19.6589 76 C 24.5661 17.6938 10.6435 151 O 18.8343 15.2787 23.6940 152 O 14.2319 17.7741 23.4245 227 H 27.6734 14.0442 21.0343 228 H 29.3473 15.3065 22.4077 270 H 19.6392 14.6041 8.5137 271 H 18.3387 13.8848 6.4681 29 Ru 11.15770 10.44856 11.19777 30 Ru 10.93752 10.33843 15.45045 105 C 14.51689 6.13970 14.44692 106 C 7.48658 17.50412 8.94044 181 H 14.24158 9.85907 9.51728 182 H 15.73085 14.72095 7.94740 255 H 20.16889 20.09227 10.59239 256 H 19.37248 21.37024 11.53057 121 C 14.6278 26.0167 20.1907 122 C 8.2617 7.9326 25.5261 197 H 8.6957 15.0292 17.8323 198 H 18.8974 15.0781 25.5790 273 H 13.7514 10.9988 2.5660 274 H 13.7835 13.9867 3.3487 349 H 32.1009 13.5382 10.2890 350 H 31.2556 14.2934 8.9226 101 C 13.3564 11.1062 6.2042 102 C 14.7770 11.4415 6.6686 177 H 24.3796 20.1876 12.2339 178 H 24.6102 18.5630 11.6237 253 H 26.5370 16.1413 17.7538 254 H 26.1212 14.5303 18.3175 302 H 26.1629 23.8858 20.9084 303 H 25.0082 24.9973 18.9706 Ru 15.3958 17.5147 21.8974 Ru 16.7699 19.8783 13.3992 95 C 16.4031 12.508 9.5746 96 C 32.4517 19.2532 12.289 171 H 16.134 21.4757 13.8247 172 H 17.9291 20.7277 22.892 235 H 29.9625 18.3554 11.4743 236 H 28.8337 17.471 13.536 Structure 69, figure 4.11 (a) -Ru 55 (C 7 H 15 COOH) 6.5890 29 Ru 13.5857 6.2953 6.6927 61 H 17.1264 14.8170 10.2054 H 12.0985 13.2078 9.6916 94 H 18.5528 5.7146 12.5684 Ru 16.6294 14.5771 17.4623 95 H 15.5484 8.7726 13.3345 Ru 10.8753 15.7557 10.8267 88 H 14.7123 19.5777 11.9270 77 C 25.9629 18.0061 10.0958 153 O 15.1848 19.8359 23.4646 229 H 28.3981 16.7970 22.2305 272 H 18.3174 12.2300 7.0708 31 Ru 12.20742 11.05152 17.57176 107 C 6.30503 18.14990 8.21293 183 H 10.86634 18.50310 11.65947 257 H 9.62885 8.11893 19.89107 123 C 8.6159 9.0817 24.5805 199 H 17.3904 16.0285 25.6315 275 H 12.9009 12.7279 4.2066 351 H 31.8617 15.2971 10.2541 103 C 14.8197 12.2798 7.9488 179 H 11.5521 20.4901 11.8627 255 H 12.2864 10.0545 4.6123 304 H 25.6813 23.7906 17.8736 Ru 15.2894 19.047 15.5275 97 C 31.2515 18.8384 13.1411 173 H 13.664 17.2407 21.4308 237 H 28.6699 19.1111 14.1606 Domain 7 -Ru 55 (CH 3 COO)(H) 54 1 Ru 15.2555 13.2301 15.2999 2 Ru 15.2729 13.4717 10.9019 3 Ru 15.3276 11.8386 13.0253 4 Ru 13.7432 15.5274 15.4535 5 Ru 13.7082 15.8514 11.0265 6 Ru 12.4808 13.1544 15.3014 7 Ru 13.9177 14.1491 13.1428 8 Ru 12.5007 13.4572 10.9044 9 Ru 12.6620 11.8028 12.9668 10 Ru 12.4181 16.4222 13.3098 11 Ru 11.2446 14.0344 13.1317 12 Ru 8.4929 13.9587 13.0340 13 Ru 9.7098 16.1812 13.3189 14 Ru 9.7572 11.5249 12.9931 15 Ru 10.9190 18.4563 13.4106 16 Ru 11.1075 14.2194 8.9469 17 Ru 9.9279 13.1754 11.0682 18 Ru 9.8999 13.0055 15.0525 19 Ru 11.1262 13.6488 17.3412 20 Ru 12.3231 16.6074 9.0538 21 Ru 11.0532 15.6590 11.1695 22 Ru 11.0925 15.3761 15.3477 23 Ru 12.3746 16.0402 17.5251 24 Ru 12.3097 18.0309 11.2352 25 Ru 13.5239 18.8701 13.4586 26 Ru 12.3594 17.7410 15.5411 27 Ru 11.3017 9.3038 12.8866 28 Ru 12.5693 12.0121 8.8170 29 Ru 11.2713 11.0721 10.9255 30 Ru 11.3167 10.8329 14.9008 31 Ru 12.4967 11.3871 17.2289 32 Ru 13.7504 14.3452 8.8222 33 Ru 13.7917 13.7362 17.4817 34 Ru 14.9544 16.7477 9.0278 35 Ru 15.0756 16.5684 13.3038 36 Ru 14.9807 16.1600 17.5743 37 Ru 14.8514 18.1099 11.2916 38 Ru 14.8684 17.8364 15.5137 39 Ru 14.0480 9.4513 12.9950 40 Ru 12.5530 8.7073 15.1698 41 Ru 15.1620 12.1892 8.7560 42 Ru 14.0164 11.0953 10.8664 43 Ru 13.9316 10.8974 15.0789 44 Ru 15.2825 11.5844 17.1914 45 Ru 16.3852 14.5193 8.8823 46 Ru 16.5579 14.3505 13.1684 47 Ru 16.4577 13.9355 17.3930 48 Ru 16.3881 15.9657 11.1688 49 Ru 16.3720 15.6681 15.3430 50 Ru 16.5452 9.6438 12.8267 51 Ru 16.6533 11.3206 10.7539 52 Ru 18.0127 11.9118 12.9315 53 Ru 16.6563 11.0489 15.0575 54 Ru 17.7996 13.7629 10.9973 55 Ru 17.7755 13.3978 15.1688 56 C 12.3887 7.4475 19.3396 57 C 12.4486 8.4245 18.1957 58 O 12.3625 7.9145 17.0099 59 O 12.5810 9.6580 18.4529 60 H 6.8862 13.9433 13.1067 61 H 10.5115 8.0106 13.4634 62 H 8.0086 15.5872 13.4961 63 H 9.5970 17.7051 14.3580 64 H 8.3081 12.4553 12.0700 65 H 9.4855 13.2475 16.7969 66 H 10.5714 15.9807 9.3518 67 H 9.6504 17.7316 12.3489 68 H 9.4616 13.6701 9.4208 69 H 10.5974 15.4230 17.1674 70 H 11.7902 18.2241 9.5046 71 H 12.0243 19.5081 12.3749 72 H 11.7441 17.6708 17.2343 73 H 11.1897 12.7454 7.9278 74 H 10.5127 9.4813 11.2626 75 H 11.4933 10.5850 9.2367 76 H 9.6507 9.6848 13.2633 77 H 11.0071 10.7020 16.7099 78 H 12.3657 15.0986 7.8394 79 H 12.4095 14.3771 18.5329 80 H 13.6230 17.4871 8.1295 81 H 13.6773 16.8624 18.5160 82 H 14.8275 19.5019 12.4388 83 H 15.2510 18.3952 9.5334 84 H 16.6544 17.6478 11.6154 85 H 14.7670 19.4031 14.6121 86 H 13.9493 10.7784 8.9673 87 H 12.8173 9.6352 11.7028 88 H 14.1637 9.1299 15.4814 89 H 13.8802 12.0992 18.3464 90 H 15.1122 15.2789 7.8122 91 H 16.5973 12.3592 18.2007 92 H 18.0964 15.5324 11.3580 93 H 15.3909 17.8532 17.2354 94 H 15.4416 8.3171 13.1613 95 H 16.6160 11.1228 8.9832 96 H 15.4776 9.9459 10.8896 97 H 18.2372 10.2264 12.4299 98 H 16.4697 10.3483 16.6935 99 H 17.2750 9.3664 14.3329 100 H 18.0794 14.1150 9.2614 101 H 18.3943 12.0168 11.0949 102 H 18.4605 13.5885 13.3629 103 H 18.4694 11.6115 14.6250 104 H 8.1063 12.9886 14.3618 Roberto González Gómez 404 Domain 8 -Ru 55 (CH 3 COO)(H) 71 1 Ru 15.2024 13.2106 15.2851 2 Ru 15.1739 13.3197 10.9700 3 Ru 15.1293 11.6714 13.1346 4 Ru 13.7584 15.5301 15.4503 5 Ru 13.6826 15.6656 11.0139 6 Ru 12.4252 13.1421 15.3901 7 Ru 13.8348 14.0445 13.1569 8 Ru 12.3638 13.2476 11.0147 9 Ru 12.4762 11.6854 13.1286 10 Ru 12.4189 16.3614 13.2622 11 Ru 11.1192 13.9436 13.2004 12 Ru 8.3776 14.0824 13.2334 13 Ru 9.6948 16.2274 13.3846 14 Ru 9.6231 11.5844 13.1543 15 Ru 10.9056 18.4091 13.3961 16 Ru 11.0323 14.0795 9.0175 17 Ru 9.7105 13.2782 11.1175 18 Ru 9.7815 13.1793 15.3000 19 Ru 11.1230 13.8194 17.4386 20 Ru 12.3079 16.3995 9.0337 21 Ru 11.0038 15.6025 11.2389 22 Ru 11.1266 15.4448 15.3143 23 Ru 12.4300 16.1353 17.5028 24 Ru 12.3305 17.9420 11.2190 25 Ru 13.6541 18.8705 13.3539 26 Ru 12.3766 17.7929 15.4862 27 Ru 11.0651 9.3004 13.1584 28 Ru 12.3840 11.8341 8.8941 29 Ru 11.0844 10.9261 11.0538 30 Ru 11.1044 10.9016 15.2016 31 Ru 12.3574 11.4938 17.4381 32 Ru 13.6757 14.1470 8.8715 33 Ru 13.7686 13.8146 17.5382 34 Ru 14.9290 16.4211 8.9129 35 Ru 15.0600 16.3915 13.2114 36 Ru 15.0376 16.1969 17.5105 37 Ru 15.0172 18.0527 11.1271 38 Ru 15.0310 17.7686 15.3708 39 Ru 13.7391 9.2930 13.1879 40 Ru 12.5210 8.7728 15.5188 41 Ru 15.0238 11.8586 8.8738 42 Ru 13.7850 10.8895 10.9930 43 Ru 13.8059 10.8482 15.2232 44 Ru 15.0859 11.5498 17.4552 45 Ru 16.3177 14.1621 8.8303 46 Ru 16.4669 14.1017 13.1352 47 Ru 16.4012 13.9349 17.4218 48 Ru 16.4352 15.7083 11.0342 49 Ru 16.4506 15.5619 15.3319 50 Ru 16.4312 9.5106 13.1082 51 Ru 16.4730 10.9672 10.9944 52 Ru 17.9533 11.7631 13.1223 53 Ru 16.4991 10.8669 15.2139 54 Ru 17.6938 13.3607 10.9532 55 Ru 17.7404 13.2576 15.2819 56 C 12.6647 7.6855 19.7468 57 C 12.5504 8.6201 18.5740 58 O 12.3290 9.8465 18.7900 59 O 12.7061 8.0826 17.4017 60 H 6.7791 14.1896 13.2917 61 H 14.0093 20.4295 13.3637 62 H 10.3921 7.8431 13.0753 63 H 15.8001 19.3726 10.6703 64 H 7.9282 15.7270 13.3973 65 H 8.0138 12.2874 13.1572 66 H 9.2303 17.9921 13.5139 67 H 8.0323 13.9542 11.5255 68 H 9.3568 13.6409 9.3949 69 H 8.0347 13.7469 14.9027 70 H 9.6196 16.3993 10.9719 71 H 10.6442 15.6184 17.1545 72 H 11.8966 17.7934 17.2063 73 H 10.8170 18.8124 11.6469 74 H 11.8417 18.0434 9.4722 75 H 12.2354 19.7871 13.2803 76 H 10.9637 18.8897 15.0940 77 H 9.3636 9.7680 13.2851 78 H 10.5467 9.1531 11.5437 79 H 10.9641 10.8831 9.2340 80 H 11.1546 12.3525 18.4487 81 H 10.8645 10.7608 17.0029 82 H 13.5621 17.1982 8.0471 83 H 13.7522 16.9119 18.4927 84 H 15.0083 18.1760 9.3825 Roberto González Gómez 405 106 H 19.0653 12.2784 14.3115 107 H 17.8091 11.6555 16.0663 108 H 9.3059 11.4044 11.3583 109 H 9.2537 11.3616 14.8821 131 H 12.4223 8.2026 20.6792 132 H 13.6963 7.3066 19.7924 133 H 16.7637 17.3317 15.1366 Domain 5 -Ru 55 (H) 70 1 Ru 17.6621 8.6171 10.8969 2 Ru 17.6788 8.5871 6.6038 3 Ru 17.6113 7.0102 8.7904 4 Ru 16.2315 10.8846 11.0004 5 Ru 16.2067 10.9508 6.5707 6 Ru 14.8762 8.5483 10.9692 7 Ru 16.3064 9.3765 8.7484 8 Ru 14.8526 8.5242 6.6346 9 Ru 14.9256 7.0294 8.8207 Ru 14.9373 11.7314 8.7869 Ru 13.6024 9.3229 8.7736 Ru 10.8257 9.5253 8.7346 Ru 12.2126 11.6274 8.9133 Ru 12.0210 7.0142 8.7601 Ru 13.4580 13.8128 8.8515 Ru 13.5586 9.3405 4.5954 Ru 12.1907 8.6354 6.6928 Ru 12.1648 8.7148 10.8512 Ru 13.5366 9.2691 12.9929 Ru 14.8654 11.6465 4.5571 Ru 13.5207 10.9314 6.7766 Ru 13.5987 10.8895 10.8411 Ru 14.8816 11.5871 13.0181 Ru 14.8707 13.2413 6.7001 Ru 16.1921 14.2547 8.8077 Ru 14.9362 13.2120 10.9688 Ru 13.4534 4.7107 9.0035 28 Ru 14.8707 7.0751 4.5422 29 Ru 13.5288 6.2648 6.7211 30 Ru 13.3075 6.4235 10.9057 31 Ru 14.8513 6.9249 12.9763 32 Ru 16.1992 9.3653 4.4757 33 Ru 16.1887 9.2643 13.1338 34 Ru 17.4805 11.6341 4.4601 35 Ru 17.5805 11.7433 8.7896 36 Ru 17.5017 11.6251 13.0528 37 Ru 17.5656 13.3160 6.6393 38 Ru 17.4802 13.1372 10.9054 39 Ru 16.1525 4.6373 8.9443 40 Ru 14.8314 4.5437 11.3836 41 Ru 17.5255 7.0665 4.5489 42 Ru 16.2332 6.2005 6.6794 43 Ru 16.4049 6.2468 10.8973 44 Ru 17.5421 6.9668 13.1479 45 Ru 18.8373 9.3561 4.4587 46 Ru 18.9700 9.4077 8.7449 47 Ru 18.8258 9.3322 13.0440 48 Ru 18.9451 10.9707 6.6220 49 Ru 18.9201 10.8960 10.8984 50 Ru 18.8584 4.8109 8.8298 51 Ru 18.9335 6.1939 6.6887 52 Ru 20.4173 7.0459 8.7863 53 Ru 18.9454 6.2291 10.9239 54 Ru 20.1937 8.5993 6.5908 Roberto González Gómez 406 76 H 13.4992 7.7234 13.8659 77 H 13.7335 5.5135 12.6285 78 H 16.1354 12.4031 3.5569 79 H 16.2193 12.3916 13.9802 80 H 17.5885 13.3889 4.8861 81 H 15.9606 14.7737 10.4083 82 H 18.0465 13.2408 12.6263 83 H 16.2124 7.7288 3.4224 84 H 16.5501 4.5463 7.2331 85 H 16.3158 5.7283 4.8804 86 H 17.7601 6.0434 14.4369 87 H 19.2833 11.1652 4.8070 88 H 18.8164 7.8187 3.5539 89 H 18.9085 7.7277 13.9326 90 H 18.3724 14.1639 7.7392 112 H 14.8470 5.1668 6.3091 113 H 13.1969 3.9587 10.4990 114 H 17.5208 10.1775 3.3613 115 H 17.7493 14.4102 9.5688 116 H 17.5366 10.0807 14.1694 117 H 19.2291 12.7777 6.5214 118 H 14.7271 3.6443 8.4533 119 H 16.2689 5.6574 12.8804 120 H 15.7827 3.4991 10.3296 121 H 16.1976 7.6715 14.1676 122 H 19.3221 11.1252 12.6825 123 H 20.6229 10.3396 6.7132 124 H 19.4073 11.2791 8.2864 125 H 21.3262 8.2791 7.9973 Domain 41 -Ru 55 (CH 3 COO) 16 (H) 33 1 Ru 15.1588 12.7918 15.7157 2 Ru 15.0758 12.679 11.3357 3 Ru 15.1448 11.1643 13.5127 4 Ru 13.802 15.0995 15.7323 5 Ru 13.6115 15.015 11.4085 6 Ru 12.4563 12.6223 15.7381 7 Ru 13.7843 13.472 13.5756 8 Ru 12.3438 12.6443 11.4709 9 Ru 12.432 11.0278 13.6009 10 Ru 12.3658 15.7815 13.5551 11 Ru 11.1208 13.364 13.6045 12 Ru 8.5033 13.4368 13.8341 13 Ru 9.73 15.5813 13.6022 14 Ru 9.657 10.9805 13.7561 15 Ru 10.8773 17.8425 13.6614 16 Ru 10.8733 13.2288 9.4206 17 Ru 9.7038 12.5038 11.7315 18 Ru 9.8158 12.677 15.7495 19 Ru 11.1338 13.4998 17.8591 20 Ru 12.395 15.783 9.3306 21 Ru 10.9408 14.8633 11.4455 22 Ru 11.1115 14.9535 15.6289 23 Ru 12.493 15.7698 17.9153 24 Ru 12.1265 17.3008 11.4221 25 Ru 13.5078 18.1478 13.5556 26 Ru 12.3935 17.2848 15.6616 27 Ru 11.1685 8.7485 13.7493 28 Ru 12.3573 11.193 9.3012 29 Ru 11.046 10.3443 11.5869 30 Ru 11.1515 10.3097 15.8301 Roberto González Gómez 407 52 Ru 17.8453 11.158 13.4121 53 Ru 16.5358 10.5858 15.6502 54 Ru 17.6685 12.8297 11.4192 55 Ru 17.8368 12.703 15.6216 56 C 5.2472 10.6102 13.4017 57 C 6.6165 11.2238 13.5351 58 C 14.0865 12.1698 22.0324 59 C 14.232 12.2703 20.5351 60 C 20.6135 13.6003 8.2597 61 C 19.316 13.3288 8.977 62 C 7.338 15.7728 9.0171 63 C 8.624 15.1543 9.4994 64 C 9.9653 20.6655 16.8784 65 C 10.5025 19.4998 16.0956 66 C 19.245 18.21 14.3231 67 C 18.0125 17.4995 14.8216 68 C 16.2465 5.4383 15.5529 69 C 15.1795 6.4023 15.1224 70 C 13.3608 9.3088 5.5214 71 C 13.4833 9.95 6.8778 72 C 21.805 10.8738 15.2456 73 C 20.3825 11.2798 14.9666 74 C 8.5078 6.8285 10.8163 75 C 9.457 7.8015 11.4717 76 C 10.045 15.6878 21.5322 77 C 10.664 15.3193 20.2085 78 C 10.2278 7.7608 19.4056 79 C 10.8342 8.8005 18.4967 80 C 15.8223 19.655 7.7446 81 C 15.5415 18.5165 8.6915 82 C 16.502 19.7473 19.0094 83 C 15.908 18.629 18.1906 84 C 12.2493 21.6985 11.311 85 C 12.4317 20.268 11.7445 86 C 13.0145 14.856 5.1095 87 C 13.0635 14.774 6.6136 88 O 6.679 12.5093 13.5626 89 O 7.6208 10.4373 13.5975 90 O 13.8557 13.35 19.9696 91 O 14.6993 11.2475 19.9173 92 O 18.2285 13.573 8.3478 93 O 19.3723 12.8898 10.1735 94 O 9.1783 15.672 10.5282 95 O 9.0658 14.1328 8.8657 96 O 11.2925 18.6878 16.7029 97 O 10.1697 19.383 14.8668 98 O 16.9538 18.1783 15.0046 99 O 18.1103 16.2328 15.0098 100 O 14.163 6.561 15.879 101 O 15.3388 7.0298 14.0028 102 O 14.6475 10.1408 7.352 103 O 12.3867 10.2413 7.4911 104 O 19.85 12.148 15.7409 105 O 19.7818 10.712 13.987 106 O 9.929 7.478 12.6126 128 H 13.917 9.9612 17.5471 129 H 16.5983 16.8403 11.6085 130 H 12.541 7.8615 13.0268 131 H 16.0595 12.0518 8.0826 132 H 16.5395 10.2472 9.5035 133 H 16.6473 12.0288 18.5611 134 H 16.9523 15.3483 17.3394 135 H 18.2318 12.9305 13.8772 136 H 17.2195 8.969 15.1541 137 H 5.2795 9.5375 13.6144 138 H 4.8888 10.7635 12.3731 139 H 4.5425 11.1153 14.0738 140 H 14.7968 11.445 22.444 141 H 13.0665 11.8248 22.2604 142 H 14.223 13.1545 22.4936 143 H 21.3795 12.8838 8.5774 144 H 20.959 14.609 8.5327 145 H 20.4712 13.5645 7.1744 146 H 7.1393 15.4925 7.9773 147 H 7.38 16.8628 9.1265 148 H 6.5155 15.4023 9.6473 149 H 9.0608 21.0643 16.4081 150 H 10.7308 21.456 16.899 151 H 9.7673 20.367 17.9148 152 H 20.132 17.8597 14.865 153 H 19.1323 19.2943 14.4199 154 H 19.383 17.9578 13.2613 155 H 16.7675 5.0175 14.6861 156 H 15.816 4.6478 16.1767 157 H 16.9803 5.9915 16.1593 158 H 12.5058 9.7305 4.9806 159 H 13.178 8.2318 5.6516 160 H 14.2863 9.4393 4.9512 161 H 17.9425 14.5955 11.707 162 H 17.018 8.7538 11.8888 163 H 13.401 17.1695 9.9913 164 H 10.7448 15.2883 17.3748 165 H 11.279 17.0535 9.782 166 H 13.8435 16.2835 18.8653 167 H 9.3575 13.2543 17.3272 168 H 18.1785 10.9735 11.5944 169 H 22.275 10.4695 14.3429 170 H 21.8028 10.091 16.0194 171 H 22.3725 11.7273 15.6338 172 H 9.7527 9.2748 14.6242 173 H 8.2703 7.1465 9.7965 174 H 7.5835 6.7738 11.4088 175 H 8.952 5.8248 10.8077 176 H 18.1635 13.2123 17.2965 177 H 9.108 15.1418 21.6853 178 H 9.8803 16.7698 21.5881 179 H 10.7445 15.411 22.335 180 H 14.428 9.5765 9.9224 181 H 10.7923 7.6865 20.3406 182 H 10.1963 6.7895 18.8968 Roberto González Gómez 408 Domain 35 -Ru 55 (CH 3 COO) 12 (H) 65 1 Ru 15.3368 13.343 15.2235 2 Ru 15.402 13.3393 10.8927 3 Ru 15.3955 11.8123 13.0946 4 Ru 13.932 15.6608 15.3192 5 Ru 13.9 15.6448 10.9127 6 Ru 12.6212 13.2563 15.2521 7 Ru 13.9845 14.1218 13.1071 8 Ru 12.5713 13.3895 10.9286 9 Ru 12.545 11.7393 13.0055 10 Ru 12.6958 16.4737 13.1537 11 Ru 11.2048 14.0355 13.143 12 Ru 8.6255 13.999 12.922 13 Ru 9.7928 16.229 13.2824 14 Ru 9.8903 11.675 13.1349 15 Ru 11.0938 18.4395 12.8534 16 Ru 11.2385 14.0773 8.8049 17 Ru 10.0155 13.2035 11.0084 18 Ru 9.8132 13.363 15.2402 19 Ru 11.204 13.997 17.452 20 Ru 12.8067 16.4405 8.7422 21 Ru 11.1515 15.7245 11.1199 22 Ru 11.2483 15.6233 15.229 23 Ru 12.5208 16.3845 17.4304 24 Ru 12.7415 17.9138 10.9091 25 Ru 13.721 18.866 13.1271 26 Ru 12.2345 18.0348 15.2526 27 Ru 11.3882 9.4367 13.0616 28 Ru 12.599 11.887 8.6954 29 Ru 11.2588 11.0385 10.895 30 Ru 11.3165 10.8915 15.1772 31 Ru 12.6705 11.6828 17.3924 32 Ru 13.9215 14.0388 8.8429 33 Ru 13.9655 14.009 17.4385 34 Ru 15.3183 16.323 8.9071 35 Ru 15.3263 16.4532 13.1394 36 Ru 15.1825 16.427 17.3909 37 Ru 15.1963 17.919 11.0456 38 Ru 15.1405 18.042 15.236 39 Ru 14.033 9.5768 13.0809 40 Ru 12.9505 8.74 15.2264 41 Ru 15.2718 11.8888 8.7339 42 Ru 14.0005 11.0565 10.9182 43 Ru 13.922 11.0203 15.1453 44 Ru 15.2445 11.813 17.2736 45 Ru 16.564 14.123 8.7979 46 Ru 16.6318 14.1523 13.1326 47 Ru 16.521 14.2047 17.2944 48 Ru 16.62 15.6453 11.0448 49 Ru 16.6978 15.7905 15.3132 50 Ru 16.4898 9.5258 12.9748 51 Ru 16.6368 11.0455 10.9665 52 Ru 18.0625 11.61 13.1253 53 Ru 16.523 10.734 15.2789 54 Ru 17.947 13.4047 11.062 55 Ru 17.9548 13.293 15.2519 56 C 16.4213 6.5455 16.8119 57 C 15.7585 7.7763 16.2417 58 C 19.445 18.3073 12.9074 59 C 18.224 17.5623 13.3645 60 C 13.9365 9.21 5.5162 61 C 13.9573 10.1685 6.6768 62 C 7.9318 19.1433 15.7232 63 C 9.282 18.8142 15.1562 64 C 20.8305 13.7388 7.7451 65 C 19.554 13.6968 8.5457 66 C 7.746 16.7858 8.4016 67 C 8.9718 16.079 8.93 68 C 5.5018 10.9948 13.1846 69 C 6.8418 11.6765 13.0811 70 C 15.1558 12.5838 21.5597 71 C 14.9503 12.7333 20.0738 72 C 22.1983 12.126 14.6203 73 C 20.701 12.2595 14.4604 74 C 10.2583 6.98 9.608 75 C 10.776 8.1135 10.453 76 C 9.4468 16.537 20.6047 77 C 10.311 16.0608 19.4613 78 C 9.4865 9.072 18.843 79 C 10.3955 9.8288 17.9072 80 O 9.285 18.3838 13.9043 81 O 10.3208 18.95 15.8475 82 O 12.8373 10.7128 7.0075 83 O 15.0718 10.3988 7.2496 84 O 17.204 17.5313 12.5723 Roberto González Gómez 409 106 H 12.4118 18.079 17.0742 107 H 11.612 12.7652 18.5432 108 H 8.3395 13.7958 11.134 109 H 8.206 13.4925 15.2727 110 H 9.8023 13.1612 9.2531 111 H 11.2788 15.8465 9.3886 112 H 12.5217 14.8133 18.3716 113 H 12.2638 19.4238 11.9322 114 H 14.7803 19.4995 11.8799 115 H 13.2038 19.507 14.6869 116 H 10.0645 10.1735 12.0643 117 H 11.237 12.6655 7.7667 118 H 13.619 10.4878 9.3418 119 H 11.2738 8.8888 14.8619 120 H 14.081 17.1435 7.7979 121 H 13.9165 17.0695 18.4246 122 H 13.9828 10.5198 17.6054 123 H 15.3035 19.1935 13.9058 124 H 15.5208 15.113 18.5263 125 H 15.7928 18.028 9.3704 126 H 15.4888 18.154 16.9671 127 H 11.171 12.507 16.3935 128 H 12.888 8.1485 13.631 129 H 16.8858 11.2885 9.1538 130 H 15.3935 9.913 10.4967 131 H 16.8528 11.011 16.991 132 H 18.3907 14.8843 15.5568 133 H 18.3148 15.1708 11.1852 134 H 18.035 13.2845 17.0123 135 H 18.3635 13.5018 13.4779 157 H 20.7948 12.9603 6.9698 158 H 10.844 16.453 16.6668 159 H 7.38 16.298 7.4927 160 H 8.0103 17.828 8.1708 161 H 6.9665 16.8028 9.1728 162 H 9.339 11.674 14.872 163 H 4.7008 11.6592 12.843 164 H 5.3178 10.7485 14.2412 165 H 5.5048 10.0608 12.6126 166 H 12.6198 14.8438 7.7347 167 H 14.6358 13.3788 22.1026 168 H 16.229 12.6013 21.789 169 H 14.7665 11.6065 21.8798 170 H 12.266 18.0818 9.1915 171 H 22.6025 11.4068 13.9012 172 H 22.4322 11.8125 15.646 173 H 22.6668 13.1075 14.462 174 H 17.111 15.938 9.2932 175 H 10.4743 7.1545 8.5488 176 H 9.1657 6.928 9.7347 177 H 10.6808 6.026 9.9424 178 H 15.2845 8.2665 12.7803 179 H 8.6467 15.8193 20.8114 180 H 9.0213 17.519 20.3601 181 H 10.07 16.6653 21.5004 182 H 16.1197 12.9445 7.5478 183 H 8.783 8.451 18.2796 184 H 8.9198 9.796 19.4459 185 H 10.0803 8.4585 19.5312 186 H 16.9805 16.2237 17.0768 Ru 10.8329 15.5372 15.8091 Ru 12.0763 16.4033 17.9066 Ru 12.1273 17.8508 11.6606 Ru 13.3715 18.7828 13.6816 Ru 12.0579 17.9555 15.8785 Ru 11.1178 9.4281 13.8998 Ru 12.4195 11.7712 9.5533 Ru 11.067 10.9936 11.6508 Ru 11.0271 11.0195 15.8278 Ru 12.2618 11.8263 17.9178 Ru 13.6239 14.023 9.5794 Ru 13.5108 14.0959 18.0634 Ru 14.8136 16.2799 9.5141 Ru 14.9121 16.6101 13.8337 Ru 14.62 16.5029 18.0715 Ru 14.6785 17.9445 11.7012 Ru 14.4688 18.023 15.9611 Ru 13.8599 9.5982 13.8438 Ru 12.5169 8.8328 15.7744 Ru 15.0155 11.714 9.667 Ru 13.7352 11.07 11.6908 Ru 13.6588 11.0203 15.9446 Ru 14.8659 11.9065 17.9603 Ru 16.1754 14.3019 9.5262 Ru 16.4047 14.1942 13.8631 Ru 16.0458 14.468 18.0426 Ru 16.1798 15.7002 11.6494 Ru 16.2043 15.8247 16.014 Ru 16.3426 9.6927 13.9726 Ru 16.3677 11.1243 11.7986 Ru 17.7077 11.9227 13.8449 Ru 16.3042 11.2531 15.9342 Ru 17.6067 13.5651 11.718 Ru 17.5419 13.4112 16.0821 C 5.188 11.036 13.641 C 6.541 11.6967 13.6595 C 14.3289 12.6617 22.2158 C 14.3159 12.8156 20.7172 C 20.192 13.5883 8.1032 C 18.9972 13.6177 9.0182 C 7.6008 16.4784 8.7021 C 8.8133 15.8528 9.3377 C 9.5653 21.4385 16.6953 C 10.2041 20.2721 15.9911 C 19.0409 18.4715 14.03 C 17.7644 17.7609 14.387 C 15.8995 6.0418 15.6803 90 O 14.8603 10.7525 7.8324 91 O 12.5974 10.7255 7.805 92 O 19.6096 13.2111 16.1171 93 O 19.7192 11.8457 14.3164 94 O 10.021 8.1529 12.7392 95 O 10.1039 9.3404 10.8184 96 H 5.2834 9.9495 13.7267 97 H 4.6705 11.2911 12.7056 98 H 4.5773 11.4269 14.4659 99 H 15.2512 12.1678 22.5422 100 H 13.4803 12.0269 22.5131 101 H 14.2131 13.6358 22.7027 102 H 21.0271 13.0623 8.5764 103 H 20.4984 14.6235 7.8907 104 H 19.9284 13.119 7.1478 105 H 7.5479 16.2335 7.6367 106 H 7.6253 17.5654 8.848 107 H 6.699 16.1001 9.2061 108 H 8.5914 21.6678 16.2498 109 H 10.2128 22.3212 16.5819 110 H 9.464 21.2258 17.7652 111 H 19.7354 18.4772 14.8764 112 H 18.8255 19.4956 13.7007 113 H 19.5072 17.9429 13.1852 114 H 16.5062 5.7488 14.8168 115 H 15.4132 5.1694 16.1302 116 H 16.5677 6.4841 16.436 117 H 12.7764 9.7743 5.4877 118 H 14.1294 8.7585 6.0696 119 H 14.4863 10.2994 5.2752 120 H 17.9393 15.3233 11.8457 121 H 16.4309 10.6464 10.0624 122 H 13.5502 17.0737 8.4602 123 H 10.9091 15.5496 18.9627 124 H 11.5752 17.9388 9.9145 125 H 13.3377 17.2052 19.0495 126 H 9.1822 13.5532 17.4936 127 H 18.1305 11.7253 12.063 128 H 22.194 11.7356 14.7129 129 H 21.8851 11.745 16.478 130 H 22.2072 13.2729 15.6475 131 H 17.7862 14.0408 17.7464 132 H 8.8787 7.4299 9.7392 133 H 7.9469 7.1998 11.2529 134 H 9.4235 6.261 10.9936 135 H 8.9807 17.8875 13.5047 3 Ru 12.2477 7.1318 8.7968 4 Ru 13.5503 13.9180 8.7740 5 Ru 13.5412 9.4002 4.6399 6 Ru 12.2754 8.6542 6.7043 7 Ru 13.5666 9.4493 8.7722 8 Ru 12.2215 8.7222 10.7934 9 Ru 13.5420 9.4426 12.8963 10 Ru 14.8758 11.7085 4.6093 11 Ru 13.5620 10.9475 6.6584 12 Ru 14.9422 11.7665 8.7781 13 Ru 13.5627 10.9654 10.8637 14 Ru 14.8537 11.7023 12.9068 15 Ru 14.8603 13.2041 6.7012 16 Ru 16.1952 14.0318 8.7306 17 Ru 14.8608 13.2387 10.8360 18 Ru 13.5838 4.9205 8.8022 19 Ru 14.8748 7.1414 4.6440 20 Ru 13.5816 6.3891 6.6991 21 Ru 14.8712 7.1135 8.7751 22 Ru 13.5912 6.3992 10.8269 23 Ru 14.8978 7.1291 12.9477 24 Ru 16.1593 9.4286 4.5482 25 Ru 14.8992 8.6943 6.6393 26 Ru 16.2686 9.4567 8.7912 27 Ru 14.8805 8.6479 10.9447 28 Ru 16.1363 9.3995 13.0018 31 Ru 17.6195 11.8606 8.7913 32 Ru 16.2719 10.9841 10.9529 33 Ru 17.4632 11.6387 30 Ru 13.3561 6.3511 10.8092 31 Ru 14.8232 6.9274 12.9458 62 H 13.8123 5.7191 5.0105 63 H 14.7044 8.3692 14.1298 H 10.6862 7.9121 7.6875 H 11.7737 8.9645 12.3347 95 H 19.5038 4.6637 10.3099 96 H 20.6065 9.0688 5.0760 Ru 16.7596 16.3223 11.1393 Ru 16.6608 16.2793 15.3582 96 H 16.9224 11.3245 9.2004 97 H 15.7433 10.3064 11.0791 Ru 10.8081 15.6655 15.0309 Ru 12.0895 16.3598 17.2073 89 H 15.1832 18.2691 9.1599 90 H 16.5639 17.5439 11.2375 1 Ru 14.7763 13.6443 15.8379 55 Ru 17.2856 13.5501 15.8674 78 C 25.9761 18.3053 8.5969 79 C 24.6088 17.3966 12.1396 154 H 22.0966 18.6180 15.6272 155 H 19.2879 13.2270 15.0422 230 H 27.7395 15.4311 23.1515 231 H 23.9818 21.2238 17.9874 273 H 20.1455 12.5218 5.3796 274 H 20.8654 13.8203 6.3541 32 Ru 13.84420 13.56103 9.18723 33 Ru 13.52044 13.49991 17.67480 108 C 5.93037 19.51511 8.79162 109 C 7.85520 16.13688 8.36308 184 H 10.45935 16.92587 14.82201 185 H 10.47125 14.50117 22.07782 258 H 10.43039 6.82131 19.01025 259 H 8.56604 6.71574 17.35505 124 C 10.1234 9.3229 24.4696 200 H 24.7168 18.0684 11.1837 276 H 15.0782 11.5635 4.7227 352 H 29.6301 13.1781 10.5200 104 C 16.2347 12.6357 8.4154 180 H 10.7650 20.3616 13.4410 256 H 13.8058 10.8087 4.0889 305 H 24.4874 21.9692 19.1477 Ru 15.3143 19.1191 19.7028 98 C 29.918 18.9581 12.3988 174 H 22.6919 15.2366 15.9563 238 H 27.2426 19.7323 12.1932 Domain 73 -Ru 55 (C 7 H 15 COO) 14 (H) 14 125 C 10.5082 10.4690 23.5296 201 H 23.9523 16.8921 10.1138 277 H 15.9537 12.8410 3.8812 353 H 30.2270 14.1878 11.8333 105 C 16.2414 13.4722 9.6973 181 H 14.5999 26.5727 20.9556 257 H 13.8411 9.3173 5.0494 306 H 23.8245 23.1655 20.2493 Ru 16.6481 19.7991 21.9053 99 C 28.7063 18.5231 13.2264 175 H 14.2926 13.4327 16.6072 239 H 27.4222 18.1066 11.5369 Ru 10.9363 10.4615 13.5803 Ru 17.4513 7.9740 17.6779 Ru 9.1549 12.9894 10.2290 Ru 15.9864 10.5022 13.6741 Ru 9.8358 12.0302 13.4472 Ru 15.1170 7.3535 13.4649 Ru 9.0307 13.3890 11.9200 Ru 14.3848 8.8338 11.3269 13.0537 34 Ru 17.4657 13.1897 32 Ru 16.0814 9.4809 4.5823 64 H 14.6599 5.0603 13.0937 H 13.1522 11.1640 4.8163 97 H 20.7949 7.0711 6.9733 Ru 16.6696 10.0842 13.0754 98 H 18.4274 10.5649 12.7795 Ru 12.1935 18.0641 10.8581 91 H 14.7466 19.4871 14.1498 2 Ru 14.8945 13.6624 11.4539 56 C 10.0092 6.6076 16.0395 80 C 23.2878 17.1742 12.8450 156 H 17.6810 20.6922 12.2264 232 H 23.2560 22.4816 18.9698 275 H 20.8484 12.1565 6.9693 34 Ru 15.13041 15.85555 9.18678 110 C 9.05442 15.47729 9.00623 186 H 9.00132 15.21851 21.45063 260 H 7.76889 8.08664 18.11579 126 C 12.0145 10.7364 23.5052 202 H 11.6486 19.7672 10.9450 278 H 15.0360 14.5335 5.5199 354 H 29.4624 16.2447 10.5848 106 C 32.1671 20.1583 12.4560 182 H 13.5398 25.5311 21.8916 258 H 12.7946 12.0442 6.0548 307 H 20.0319 19.5045 34.0758 Ru 16.5603 21.3854 15.5966 100 C 27.3774 18.675 12.483 176 H 22.4347 17.5133 21.3466 240 H 26.2847 17.1539 13.5767 Ru 12.2670 12.6295 13.6531 Ru 18.6433 10.3963 9.3402 Ru 10.4571 15.1856 10.2726 Ru 16.5351 13.2875 5.4068 Ru 11.1648 14.1998 13.5304 Ru 13.7160 6.6305 15.3452 Ru 10.3398 15.5768 11.9899 Ru 13.1168 7.9883 13.2478 6.6635 35 Ru 17.4157 13.2236 10.9227 36 Ru 16.3458 4.9111 8.8718 37 Ru 14.9490 4.2148 10.7713 38 Ru 17.4277 7.1342 4.6019 39 Ru 16.2454 6.3757 6.6962 40 Ru 17.6339 7.1759 8.8008 41 Ru 16.2300 6.3522 10.9235 42 Ru 17.5436 7.1844 12.9169 43 Ru 18.7591 9.4625 4.5305 44 Ru 17.5634 8.6645 6.5702 45 Ru 19.0139 9.4922 8.7783 46 Ru 17.6067 8.7693 10.9589 47 Ru 18.7203 9.4748 13.0719 48 Ru 18.8033 10.9258 6.6441 49 Ru 18.8180 11.0079 10.9071 50 Ru 18.7820 4.9084 8.7935 51 Ru 18.8300 6.3916 6.7084 52 Ru 20.1957 7.1782 8.7551 53 Ru 18.8657 6.4239 10.8632 54 Ru 20.1026 8.6538 6.6619 55 Ru 20.0936 8.6539 10.9216 Domain 2 -Ru 55 (H) 17 1 Ru 17.5321 8.7095 11.0068 2 Ru 17.5076 8.6472 6.5918 3 Ru 17.5916 7.1514 8.8106 4 Ru 16.1266 10.8793 10.9981 5 Ru 16.1417 10.9699 6.6506 6 Ru 14.7497 8.5814 10.9445 7 Ru 16.2198 9.4179 8.8062 8 Ru 14.8835 8.5481 6.6838 33 Ru 16.0774 9.2642 13.0541 34 Ru 17.4442 11.6255 4.5987 35 Ru 17.4660 11.8634 8.8849 36 Ru 17.2424 11.6682 13.0779 37 Ru 17.3572 13.2081 6.7697 38 Ru 17.2028 13.2246 11.0911 39 Ru 16.2815 4.8412 8.9463 40 Ru 14.8469 4.5552 11.3856 65 H 18.7333 12.7569 5.7193 66 H 14.9821 3.6239 9.7557 67 H 18.6623 8.0774 3.4366 68 H 18.8906 6.0767 4.9023 69 H 18.8652 7.9664 14.0213 70 H 19.1425 11.2516 12.7556 71 H 21.3922 7.9471 9.9062 72 H 19.9803 5.2399 9.8883 Domain 3 -Ru 55 (H) 53 1 Ru 17.5999 8.6522 11.0012 2 Ru 17.7265 8.5796 6.6207 3 Ru 17.7054 7.1060 8.8309 4 Ru 16.1687 10.9548 11.0508 5 Ru 16.2435 11.0443 6.5750 6 Ru 14.8227 8.6577 10.8934 7 Ru 16.3381 9.4580 8.7803 8 Ru 14.9459 8.6618 6.5513 9 Ru 15.0192 7.1426 8.7146 10 Ru 14.9170 11.7891 8.8078 11 Ru 13.6645 9.4390 8.7218 12 Ru 10.9227 9.4530 8.5585 13 Ru 12.2078 11.6552 8.7135 14 Ru 12.0915 6.9603 8.6689 15 Ru 13.4861 13.8821 8.7621 16 Ru 13.6479 9.3514 4.5145 17 Ru 12.3840 8.4996 6.6855 18 Ru 12.2308 8.5609 10.6625 19 Ru 13.4542 9.2489 12.9188 20 Ru 14.9232 11.7155 4.5276 21 Ru 13.5968 10.9396 6.6556 22 Ru 13.5057 10.9193 10.8410 23 Ru 14.7622 11.6622 13.0367 24 Ru 14.8961 13.2668 6.6369 25 Ru 16.1004 14.1994 8.8528 26 Ru 14.8246 13.2400 10.9628 27 Ru 13.5557 4.7045 8.8102 28 Ru 15.0448 7.1009 4.5639 29 Ru 13.6509 6.3341 6.6954 30 Ru 13.5688 6.4124 10.6698 31 Ru 14.8617 6.9621 12.9137 32 Ru 16.3055 9.4058 4.4691 33 Ru 16.0853 9.3291 13.1043 34 Ru 17.5718 11.7858 4.5682 35 Ru 17.5590 11.8395 8.8800 36 Ru 17.3476 11.6119 13.1570 37 Ru 17.4429 13.2650 6.7474 38 Ru 17.3721 13.2043 10.9853 H 12.2152 13.1932 7.7042 H 11.9960 8.8589 4.9709 H 13.0016 11.0371 12.6645 H 14.5709 13.4030 4.8449 H 14.6898 14.8285 7.7221 H 14.2493 13.3082 12.6814 H 13.7183 7.8378 3.5806 H 12.8286 4.7450 7.1979 H 13.8701 5.7824 5.0101 H 11.9156 5.1346 9.1057 H 13.8150 5.4437 12.4390 98 H 20.8350 8.7636 9.1678 99 H 20.7762 6.8834 10.5554 100 H 10.4608 8.5416 9.9059 101 H 14.5262 14.7977 9.9538 102 H 13.3659 7.7074 13.7567 103 H 17.4422 9.9734 14.2467 104 H 14.9505 3.5252 9.4698 105 H 18.9349 8.0458 3.5995 106 H 19.3577 11.3275 5.0244 107 H 19.1822 11.1809 12.8338 108 H 20.4518 9.0152 12.6977 Domain 46 -Ru 55 (THF)(H) 53 1 Ru 15.4913 13.8912 15.3175 2 Ru 15.5934 13.8135 10.9563 3 Ru 15.5760 12.3287 13.1687 4 Ru 14.0255 16.1608 15.3913 5 Ru 14.0826 16.2654 10.9073 6 Ru 12.6965 13.8562 15.2477 7 Ru 14.1983 14.6758 13.1157 8 Ru 12.8142 13.8640 10.8917 9 Ru 12.9015 12.3452 13.0583 10 Ru 12.7722 16.9922 13.1519 11 Ru 11.5251 14.6250 13.0665 12 Ru 8.7914 14.6169 12.8980 13 Ru 10.0576 16.8364 13.0549 14 Ru 10.0037 12.1615 13.0183 15 Ru 11.3188 19.0774 13.1284 16 Ru 11.5142 14.5612 8.8504 17 Ru 10.2396 13.7118 11.0074 18 Ru 10.1050 13.7417 15.0196 19 Ru 11.3320 14.4545 17.2648 20 Ru 12.7771 16.9344 8.8727 21 Ru 11.4450 16.1367 11.0013 22 Ru 11.3651 16.1149 15.1845 23 Ru 12.6257 16.8753 17.3802 24 Ru 12.7129 18.4654 10.9949 25 Ru 13.9439 19.4233 13.1796 26 Ru 12.6899 18.4427 15.3034 Ru 16.9368 11.6481 10.9402 Ru 18.2269 12.2733 13.1390 Ru 16.8163 11.6036 15.2846 Ru 18.1228 14.0765 11.1542 Ru 18.0133 13.9030 15.2962 C 11.4797 6.4381 15.5848 C 10.5771 7.7465 17.4014 C 10.1663 6.2916 17.5738 C 10.2409 5.7506 16.1371 O 11.5387 7.7368 16.2844 H 7.1812 14.6592 12.8823 H 10.6283 8.5259 13.1544 H 8.3417 16.2908 13.1993 H 9.9471 18.3744 14.0582 H 8.5945 13.0619 12.0239 H 9.6523 14.1390 16.6991 H 11.0085 16.3700 9.1612 H 10.0408 18.4012 12.0779 H 9.8582 14.0695 9.2899 H 10.8684 16.2411 17.0181 H 12.3831 18.6091 9.2048 H 12.5068 20.0306 12.0763 H 12.0999 18.5157 17.0237 H 11.6028 13.0505 7.8950 99 H 16.5122 10.9912 16.9567 100 H 17.3248 9.8399 14.6102 101 H 18.4665 14.3001 9.4125 102 H 18.6775 12.3207 11.2993 103 H 18.6595 14.0084 13.4612 104 H 18.6499 12.0997 14.8821 105 H 8.3583 13.6777 14.2472 106 H 12.3636 20.0011 14.3107 107 H 11.2702 12.8926 18.1014 108 H 15.3231 15.1976 18.5818 109 H 12.8596 8.7001 13.9783 110 H 16.8191 13.2876 7.9437 111 H 17.2105 16.5701 9.3570 112 H 17.0527 16.4165 17.1570 113 H 18.3290 14.2358 17.0247 114 H 11.4452 6.6537 14.5107 115 H 12.4064 5.8979 15.8293 116 H 10.3275 4.6573 16.0970 117 H 9.3500 6.0472 15.5646 118 H 9.1644 6.2017 18.0122 119 H 10.8759 5.7624 18.2261 120 H 11.0893 8.1869 18.2654 121 H 9.7353 8.3907 17.1070 Ru 13.4490 18.9789 13.0109 Ru 12.2433 17.9762 15.1712 Ru 10.8408 9.4546 12.7916 Ru 12.2739 11.9406 8.6772 Ru 10.9320 11.1732 10.8274 Ru 10.8691 11.1843 14.7385 Ru 12.1486 11.6857 17.0672 Ru 13.5667 14.2328 8.6024 Ru 13.3918 14.0396 17.2467 Ru 14.8460 16.6173 8.7425 Ru 14.8779 16.6313 13.0431 Ru 14.6981 16.3781 17.2987 Ru 14.7824 18.0574 10.9432 Ru 14.6715 18.0076 15.1731 Ru 13.4811 9.5302 13.0338 Ru 11.8585 9.1600 15.5342 Ru 14.8745 12.0284 8.6415 Ru 13.6535 11.0654 10.7989 Ru 13.5027 11.0984 14.9942 Ru 14.7391 11.7710 17.0981 Ru 16.1993 14.3200 8.7112 Ru 16.2823 14.2816 13.0048 Ru 16.0346 14.0421 17.2645 Ru 16.1992 15.8461 10.9444 Ru 16.1630 15.7194 15.1199 Ru 15.9922 9.5990 12.8146 Ru 16.2974 11.1509 10.7012 Ru 17.5974 11.7724 12.8950 Ru 16.2024 11.0932 15.0355 Ru 17.5244 13.5772 10.9011 Ru 17.4306 13.3367 15.1074 C 10.3598 6.3159 15.3922 C 9.7195 7.5597 17.3566 C 9.3314 6.1023 17.5437 C 9.2100 5.6065 16.0936 C 18.8848 17.0000 16.2476 C 18.6434 17.4958 13.9073 C 20.1163 17.3066 14.2234 C 20.1706 17.6279 15.7242 O 17.9419 17.0357 15.1166 O 10.5666 7.5643 16.1552 H 6.6039 14.3513 12.7623 H 10.0360 8.0712 12.7091 92 H 13.6034 10.6702 8.9125 93 H 12.2495 8.8477 11.8911 94 H 13.5026 9.4237 15.7309 95 H 13.4133 11.2795 18.2613 96 H 14.9796 15.0853 7.5927 97 H 16.0405 12.5920 18.2074 98 H 17.8899 15.3344 11.1768 99 H 15.2491 18.0233 16.8856 100 H 14.8117 8.3225 13.1018 101 H 16.3211 10.9260 8.9523 102 H 15.0846 9.8583 10.7200 103 H 17.7183 10.0705 12.4129 104 H 15.9434 10.5086 16.7262 105 H 16.6906 9.3606 14.3382 106 H 17.8617 13.8638 9.1551 107 H 18.0363 11.8197 11.0299 108 H 18.1599 13.4305 13.3806 109 H 18.0414 11.4908 14.6091 110 H 7.7749 13.3248 14.0514 111 H 11.8765 19.5545 14.1826 112 H 10.6421 12.3901 17.8895 113 H 14.7201 14.7829 18.3653 114 H 12.0152 8.3873 13.8943 115 H 16.1923 12.8621 7.7097 116 H 16.6555 16.1020 9.1692 117 H 16.4719 15.8564 16.9800 118 H 17.7338 13.6546 16.8459 119 H 10.1588 6.6028 14.3532 120 H 11.3008 5.7493 15.4447 121 H 9.2927 4.5157 16.0071 122 H 8.2461 5.9123 15.6614 123 H 8.3986 5.9945 18.1115 124 H 10.1245 5.5577 18.0764 125 H 10.3154 7.9930 18.1682 126 H 8.8488 8.2031 17.1567 127 H 18.4171 17.5426 17.0796 128 H 19.0163 15.9448 16.5319 129 H 21.0537 17.2083 16.2227 130 H 20.1698 18.7154 15.8868 131 H 20.7562 17.9623 13.6200 132 H 20.4158 16.2646 14.0366 133 H 18.2673 16.8989 13.0682 134 H 18.3770 18.5534 13.7541 3 Ru 14.8419 12.1042 13.6512 4 Ru 13.3337 15.8818 15.9641 5 Ru 13.3870 16.1178 11.5166 6 Ru 11.9740 13.5811 15.7815 7 Ru 13.5037 14.4697 13.6593 8 Ru 12.1145 13.7288 11.4015 9 Ru 12.1930 12.1521 13.5161 10 Ru 12.0751 16.7785 13.7742 11 Ru 10.8237 14.4269 13.5921 12 Ru 8.0716 14.4272 13.4174 13 Ru 9.3538 16.6203 13.6871 14 Ru 9.2424 11.9155 13.4536 15 Ru 10.6257 18.8429 13.8208 16 Ru 10.8016 14.5117 9.3953 17 Ru 9.5383 13.5635 11.5245 18 Ru 9.3959 13.4676 15.4838 19 Ru 10.5976 14.0734 17.7986 20 Ru 12.0942 16.8670 9.5019 21 Ru 10.7374 16.0059 11.5824 22 Ru 10.6380 15.8239 15.7821 23 Ru 11.8961 16.4938 17.9803 24 Ru 12.0475 18.3257 11.6641 25 Ru 13.2352 19.2046 13.8559 26 Ru 12.0257 18.1451 15.9817 27 Ru 10.7717 9.6551 13.4094 28 Ru 12.1517 12.2492 9.3649 29 Ru 10.8407 11.4205 11.4835 30 Ru 10.7649 11.3491 15.3970 31 Ru 12.0339 11.8285 17.7545 32 Ru 13.4705 14.5530 9.3487 33 Ru 13.2323 14.1932 17.9783 34 Ru 14.7233 16.9586 9.5587 35 Ru 14.7255 16.8728 13.8505 36 Ru 14.5067 16.5488 18.0945 37 Ru 14.6043 18.3404 11.7610 38 Ru 14.4669 18.2113 15.9986 39 Ru 13.4173 9.7779 13.6630 40 Ru 11.7598 9.3194 16.1480 41 Ru 14.7813 12.3498 9.2766 42 Ru 13.5609 11.3682 11.4638 43 Ru 13.3866 11.2986 15.6630 44 Ru 14.6220 11.9467 17.7992 45 Ru 16.1015 14.6757 9.4805 46 Ru 16.1516 14.5392 13.7919 47 Ru 15.8669 14.2320 18.0190 48 Ru 16.0601 16.0871 11.7449 49 Ru 16.0089 15.9436 15.9239 50 Ru 15.9195 9.8549 13.4996 51 Ru 16.1941 11.4428 11.3945 52 Ru 17.4857 12.0248 13.6128 53 Ru 16.0911 11.2913 15.7466 54 Ru 17.4097 13.8654 11.6693 57 C 9.5532 7.9049 18.0185 58 C 9.0169 6.4971 18.2177 59 C 8.8094 6.0198 16.7716 60 C 18.7002 17.2837 17.0698 61 C 18.4736 17.7491 14.7202 62 C 19.9451 17.7859 15.1014 63 C 19.8938 18.1042 16.6026 64 C 15.0425 10.0499 6.9142 65 C 14.9842 12.2728 6.0242 66 C 14.9160 11.2959 4.8620 67 C 15.5461 10.0318 5.4706 68 O 14.7106 11.4509 7.1983 69 O 17.7789 17.2651 15.9255 70 O 10.3789 7.8140 16.8070 71 H 6.4623 14.4812 13.4763 72 H 9.9837 8.2660 13.2603 73 H 7.6292 16.1233 13.6776 74 H 9.1857 18.1624 14.6714 75 H 7.8792 12.9408 12.4404 76 H 8.9315 13.7912 17.1819 77 H 10.3066 16.2920 9.7439 78 H 9.4358 18.1317 12.6613 79 H 9.1414 14.0307 9.8311 80 H 10.1357 15.8762 17.6125 81 H 11.6194 18.5186 9.9165 82 H 11.7331 19.8469 12.7780 83 H 11.3760 18.1627 17.6691 84 H 10.8683 13.0171 8.3939 85 H 10.0101 9.7333 11.9126 86 H 10.9737 10.9660 9.7260 87 H 9.1831 10.0835 14.0103 88 H 11.6661 9.9663 17.8149 89 H 12.1321 15.3442 8.3248 90 H 11.8363 14.8034 19.0116 91 H 13.4528 17.7113 8.6043 92 H 13.1883 17.2824 19.0108 93 H 14.4441 19.8581 12.7419 94 H 15.1237 18.5932 10.0276 95 H 16.1322 17.6625 12.6839 96 H 14.5520 19.6955 14.9809 97 H 13.5135 10.9993 9.6253 98 H 12.1883 9.0214 12.5510 99 H 13.4172 9.5639 16.2534 100 H 13.3084 11.3941 18.9372 101 H 14.8798 15.4349 8.3634 102 H 15.8797 12.7603 18.9430 103 H 17.7679 15.6050 11.9930 104 H 15.0460 18.2069 17.7106 105 H 14.7342 8.5507 13.6289 106 H 16.2545 11.2012 9.6801 107 H 14.9864 10.1696 11.3110 108 H 17.6750 10.3333 13.1762 Domain 63 -Ru 55 (C 4 H 9 COO) 14 (H) 14 1 Ru 18.9684 16.8127 19.6028 2 Ru 19.1944 16.7301 15.2396 3 Ru 19.0906 15.2357 17.4502 4 Ru 17.6404 19.0447 19.5640 5 Ru 17.7244 19.1168 15.2442 6 Ru 16.2808 16.6237 19.4781 7 Ru 17.7982 17.5351 17.4055 8 Ru 16.4834 16.7505 15.2508 9 Ru 16.3115 15.0590 17.3351 10 Ru 16.3419 19.8524 17.3739 11 Ru 15.1056 17.4510 17.2819 12 Ru 12.4823 17.4309 17.1766 13 Ru 13.6764 19.5858 17.3561 14 Ru 13.5789 14.9989 17.3584 15 Ru 14.8380 21.9381 17.3439 16 Ru 15.1750 17.4317 13.1359 17 Ru 13.9121 16.6057 15.2352 18 Ru 13.6389 16.6458 19.2626 19 Ru 14.7883 17.3857 21.4338 20 Ru 16.4856 19.7957 13.1804 21 Ru 15.0105 18.9824 15.2071 22 Ru 14.9323 18.9044 19.3896 23 Ru 16.0862 19.7693 21.6053 24 Ru 16.3613 21.3193 15.3084 25 Ru 17.6221 22.1024 17.4016 26 Ru 16.1188 21.3075 19.5584 27 Ru 15.1197 12.7830 17.3797 28 Ru 16.4425 15.2558 13.1231 29 Ru 15.0979 14.4805 15.1475 30 Ru 15.0369 14.3331 19.4296 31 Ru 16.3097 15.1036 21.5366 32 Ru 17.8198 17.5507 13.1929 33 Ru 17.4875 17.4763 21.6746 34 Ru 19.0040 19.8767 13.2057 35 Ru 19.0676 19.8900 17.5126 36 Ru 18.7103 19.8149 21.7176 37 Ru 18.9374 21.4249 15.4416 38 Ru 18.5451 21.4401 19.5860 39 Ru 17.9200 12.9352 17.3699 40 Ru 16.5210 12.0869 19.1490 41 Ru 19.0434 15.2816 13.1095 42 Ru 17.8436 14.4284 15.2560 43 Ru 17.6452 14.3412 19.5073 44 Ru 18.8157 15.2299 21.5942 45 Ru 20.4177 17.7072 13.2467 46 Ru 20.4744 17.4892 17.5367 47 Ru 20.0416 17.7029 21.7401 48 Ru 20.3817 19.0192 15.3428 49 Ru 20.3093 19.0211 19.6859 50 Ru 20.3681 12.9869 17.6314 51 Ru 20.4341 14.4743 15.4635 52 Ru 21.7638 15.1785 17.5380 53 Ru 20.2801 14.5426 19.5650 54 Ru 21.7379 16.8470 15.3923 55 Ru 21.5547 16.6389 19.8107 56 C 14.4229 20.4110 26.0587 81 C 21.0144 23.5331 10.8062 82 C 21.3662 24.8261 10.0667 83 C 21.4491 24.6325 8.5518 84 C 20.9225 23.7143 12.3223 85 C 20.4123 22.4988 13.0677 86 C 26.2708 15.6641 20.7514 87 C 27.6928 15.1468 20.9886 88 C 28.3307 15.6993 22.2631 89 C 25.6659 15.0939 19.4709 90 C 24.2338 15.4802 19.1737 91 C 23.0735 22.8353 16.8276 92 C 24.3189 23.7194 16.7231 93 C 24.2864 24.6483 15.5088 94 C 23.1166 21.9060 18.0388 95 C 21.8903 21.0430 18.2425 96 C 12.1972 11.5462 22.4214 97 C 11.6734 10.4365 23.3372 98 C 10.4580 9.7100 22.7610 99 C 13.4027 12.2696 23.0185 100 C 14.1126 13.2342 22.0941 101 C 19.7755 8.3194 17.1337 102 C 20.3605 6.9060 17.1659 103 C 20.7625 6.4047 15.7777 104 C 19.4130 8.8444 18.5323 105 C 18.7011 10.1747 18.5041 106 C 11.4646 21.4500 12.8643 107 C 10.2609 22.0806 12.1604 108 C 9.8948 23.4524 12.7285 109 C 11.8309 20.0788 12.2906 110 C 13.0229 19.4216 12.9497 111 C 19.0424 13.6784 8.5036 112 C 18.9126 13.1591 7.0691 113 C 20.2653 12.8995 6.4047 114 C 17.6840 13.9408 9.1504 115 C 17.7211 14.4161 10.5854 116 C 8.1527 15.6229 15.8723 117 C 6.8595 14.8915 15.5011 118 C 5.7752 15.8278 14.9664 119 C 9.2238 14.6733 16.4084 120 C 10.5617 15.3061 16.7360 121 C 12.2734 11.2752 12.8647 122 C 11.2082 10.3138 12.3302 123 C 10.6411 10.7420 10.9763 124 C 12.8217 10.8390 14.2226 125 C 13.7765 11.8074 14.8863 126 O 14.2167 11.4891 16.0476 127 O 14.0818 12.8900 14.2798 128 O 11.5535 14.5137 16.8684 129 O 10.6197 16.5865 16.8672 130 O 16.5877 14.5618 11.1749 131 O 18.8540 14.6433 11.1371 132 O 13.7086 18.5905 12.2406 157 H 14.3517 19.1764 21.1323 158 H 15.5864 21.3401 13.7213 159 H 17.4177 20.5865 22.5851 160 H 13.2856 16.5295 21.0613 161 H 22.2034 15.0320 15.7019 162 H 13.4942 13.3299 17.8930 163 H 21.7341 17.1062 21.5446 164 H 17.9263 13.9123 13.4963 165 H 19.3406 18.5557 12.0147 166 H 16.1700 22.9062 16.4778 167 H 13.1888 21.3513 17.3865 168 H 14.4566 18.2282 26.0176 169 H 12.9572 18.9185 25.4284 170 H 14.0363 21.2272 25.4283 171 H 15.5186 20.5237 26.0505 172 H 14.2869 19.7589 28.1198 173 H 12.8002 20.4649 27.4901 174 H 13.8889 22.0312 29.1221 175 H 15.3719 22.0454 28.1444 176 H 13.8803 22.7575 27.5011 177 H 16.9009 15.9076 26.0492 178 H 18.2921 16.9443 26.2845 179 H 19.8133 14.9222 26.2934 180 H 18.4321 13.8751 25.9987 181 H 17.3918 14.6282 28.1679 182 H 18.7735 15.6781 28.4689 183 H 19.0027 13.5214 29.7354 184 H 18.9146 12.6030 28.2183 185 H 20.3025 13.6624 28.5341 186 H 20.5084 24.3994 22.4418 187 H 21.9681 23.5853 21.9165 188 H 22.0011 22.2255 24.0451 189 H 20.5075 22.9899 24.5671 190 H 21.6521 25.2374 24.5663 191 H 23.1531 24.4728 24.0505 192 H 23.1589 24.8460 26.5350 193 H 21.6825 23.8725 26.6989 194 H 23.1965 23.1059 26.1814 195 H 14.7999 25.6714 20.4914 196 H 13.6117 24.7189 21.3604 197 H 11.9647 25.0565 19.4473 198 H 13.1629 26.0187 18.5957 199 H 13.1715 27.6870 20.4871 200 H 11.9781 26.7177 21.3477 201 H 10.8555 28.6054 20.1316 202 H 11.5317 28.0362 18.5908 203 H 10.3322 27.0515 19.4497 204 H 25.2418 16.5215 12.3561 205 H 25.0885 18.2337 12.6780 206 H 23.8907 18.5429 10.4548 207 H 24.1351 16.8349 10.1043 208 H 26.6365 17.1584 10.3092 233 H 22.1731 23.4671 16.8800 234 H 22.9628 22.2360 15.9098 235 H 25.2196 23.0834 16.6789 236 H 24.4182 24.3200 17.6437 237 H 25.1823 25.2835 15.4595 238 H 24.2336 24.0722 14.5723 239 H 23.4075 25.3099 15.5401 240 H 13.1344 12.8199 23.9340 241 H 14.1684 11.5384 23.3357 242 H 12.4745 11.1217 21.4442 243 H 11.3956 12.2738 22.2154 244 H 11.4187 10.8595 24.3242 245 H 12.4844 9.7103 23.5203 246 H 10.1241 8.8962 23.4203 247 H 9.6109 10.3987 22.6246 248 H 10.6881 9.2713 21.7782 249 H 18.7716 8.1333 19.0715 250 H 20.3321 8.9688 19.1319 251 H 20.4885 9.0112 16.6597 276 H 8.8731 14.1785 17.3315 277 H 9.4212 13.8546 15.6983 278 H 8.5426 16.1531 14.9878 279 H 7.9422 16.4018 16.6216 280 H 6.4784 14.3508 16.3844 281 H 7.0830 14.1173 14.7470 282 H 4.8630 15.2767 14.6972 283 H 5.4990 16.5852 15.7152 284 H 6.1192 16.3621 14.0680 285 H 11.9993 10.6829 14.9419 286 H 13.3325 9.8638 14.1551 287 H 13.0993 11.3615 12.1408 288 H 11.8472 12.2871 12.9534 289 H 10.3883 10.2381 13.0652 290 H 11.6344 9.2993 12.2487 291 H 9.8669 10.0455 10.6243 292 H 10.1881 11.7431 11.0353 293 H 11.4292 10.7816 10.2097 Domain 64 -Ru 55 (C 4 H 9 COO) 14 (H) 31 1 Ru 14.97085 12.82586 15.61492 2 Ru 15.20918 12.73741 11.25826 3 Ru 15.10525 11.26771 13.49558 4 Ru 13.65591 15.04448 15.63677 5 Ru 13.76181 15.18018 11.25643 6 Ru 12.29270 12.65460 15.53487 7 Ru 13.79939 13.61449 13.38859 8 Ru 12.44654 12.75418 11.27812 9 Ru 12.36305 11.10236 13.33626 10 Ru 12.39551 15.86326 13.38767 35 Ru 15.02391 16.00250 13.53523 36 Ru 14.76432 15.82597 17.80785 37 Ru 15.06021 17.40775 11.35615 38 Ru 14.69918 17.41959 15.69002 39 Ru 13.96306 8.88934 13.31566 40 Ru 12.51394 8.18919 15.24498 41 Ru 15.18804 11.28300 9.09550 42 Ru 13.83088 10.41534 11.17328 43 Ru 13.64915 10.32249 15.45660 44 Ru 14.84984 11.25011 17.64977 45 Ru 16.45622 13.67120 9.23666 46 Ru 16.42474 13.57399 13.53135 47 Ru 16.14761 13.51499 17.73908 48 Ru 16.36193 15.14384 11.27468 49 Ru 16.27273 15.10459 15.66069 50 Ru 16.39318 9.03577 13.53624 51 Ru 16.50792 10.51660 11.32819 52 Ru 17.78879 11.24108 13.44856 53 Ru 16.33253 10.59052 15.60417 54 Ru 17.75935 12.91380 11.45950 55 Ru 17.65175 12.66407 15.79747 56 C 10.48901 16.68080 22.09197 57 C 9.94596 16.84657 23.51406 58 C 10.33838 18.18128 24.14893 59 C 10.09709 15.34187 21.46910 60 C 10.58935 15.10330 20.05534 61 C 14.49773 10.90296 22.50392 62 C 14.32161 10.85909 24.02389 63 C 15.09970 9.71620 24.67751 64 C 13.71523 12.04456 21.85413 65 C 13.86189 12.15467 20.34941 66 C 17.43275 19.18499 20.20288 67 C 18.21579 20.33284 20.84618 68 C 18.59459 20.05145 22.30069 69 C 17.06330 19.47381 18.74962 70 C 16.24874 18.40162 18.05843 71 C 8.84194 21.78053 15.51665 72 C 8.26969 22.96978 16.29248 73 C 7.13041 23.66879 15.54928 74 C 9.97842 21.08493 16.26473 75 C 10.54508 19.85803 15.58175 76 C 20.70134 14.01579 6.88384 77 C 22.08000 14.11193 6.22562 78 C 22.00106 14.28103 4.70758 79 C 20.78186 13.84852 8.40162 80 C 19.44796 13.67123 9.09735 81 C 16.64460 19.59885 6.48319 82 C 17.22795 20.81787 5.76324 83 C 17.49558 20.56253 4.27961 84 C 16.38926 19.86818 7.96498 85 C 15.82798 18.70961 8.76224 86 C 22.27022 11.47465 16.71963 111 C 15.04069 9.58972 4.48507 112 C 14.88059 9.12338 3.03584 113 C 16.22064 8.91097 2.33057 114 C 13.69866 9.80507 5.18176 115 C 13.78029 10.30829 6.60704 116 C 4.21578 11.57875 11.85708 117 C 2.94402 10.82796 11.45315 118 C 1.83164 11.75755 10.96674 119 C 5.31786 10.63606 12.33814 120 C 6.63184 11.29465 12.70403 121 C 8.03085 7.40586 8.95359 122 C 7.04966 6.38359 8.37285 123 C 6.56474 6.75081 6.97013 124 C 8.50050 7.02638 10.35629 125 C 9.46842 7.99209 11.00654 126 O 9.92755 7.66093 12.15681 127 O 9.78083 9.07011 10.40513 128 O 7.64190 10.52142 12.83796 129 O 6.65441 12.56987 12.86425 130 O 12.65605 10.47961 7.21978 131 O 14.92195 10.53828 7.11583 132 O 9.63684 14.54171 8.34462 133 O 9.43097 15.88223 10.15551 134 O 13.50531 6.34436 15.20053 135 O 15.00839 7.03304 13.65113 136 O 11.18146 9.57448 18.63679 137 O 10.32068 8.65470 16.75984 138 O 17.95092 16.26488 15.25614 139 O 16.82279 17.38972 13.65898 140 O 19.67802 10.74260 14.13756 141 O 19.64356 12.07958 15.97478 142 O 15.53967 18.92828 9.98597 143 O 15.67904 17.57585 8.17706 144 O 19.46507 13.23892 10.30338 145 O 18.38176 13.94998 8.45550 146 O 11.34120 19.12959 16.28716 147 O 10.20932 19.61445 14.37750 148 O 15.95344 18.61161 16.82301 149 O 15.88634 17.37136 18.70921 150 O 13.58398 13.28256 19.81390 151 O 14.23714 11.11615 19.69832 152 O 10.24187 14.00704 19.50125 153 O 11.31188 16.00871 19.50454 154 H 9.17404 17.38241 12.98197 155 H 12.53046 14.39921 7.99691 156 H 8.56240 13.28924 10.50414 157 H 9.46329 11.11309 16.08298 158 H 13.64870 18.70411 11.79380 159 H 14.52887 18.91140 14.71213 160 H 12.45713 9.38818 10.60447 161 H 10.80591 11.91174 18.24485 162 H 13.56253 9.85574 17.28196 187 H 10.12210 17.50265 21.45669 188 H 11.58645 16.77450 22.09827 189 H 10.31039 16.01711 24.14437 190 H 8.84637 16.75398 23.49911 191 H 9.93578 18.27896 25.16705 192 H 11.43209 18.28516 24.21096 193 H 9.96026 19.02895 23.55785 194 H 12.63478 11.93150 22.05512 195 H 13.99676 13.01972 22.28038 196 H 15.56772 11.00828 22.26026 197 H 14.18052 9.94598 22.06211 198 H 13.24894 10.76177 24.26472 199 H 14.64386 11.82104 24.45829 200 H 14.96127 9.70341 25.76783 201 H 14.77337 8.74036 24.28751 202 H 16.17834 9.80613 24.47902 203 H 16.48360 20.40921 18.66959 204 H 17.96349 19.64064 18.13504 205 H 18.02342 18.25643 20.25458 206 H 16.51603 18.99082 20.78188 207 H 17.61642 21.25799 20.79274 208 H 19.12861 20.52926 20.25788 209 H 19.15485 20.88802 22.74171 210 H 17.69960 19.88618 22.91915 211 H 19.22151 19.15072 22.38042 212 H 10.82199 21.77762 16.42966 213 H 9.66066 20.77174 17.27234 214 H 8.04037 21.05240 15.31314 215 H 9.20092 22.11389 14.53059 216 H 9.07534 23.69461 16.50115 217 H 7.91066 22.62445 17.27731 218 H 6.73074 24.51502 16.12576 219 H 7.46948 24.05669 14.57700 220 H 6.29893 22.97470 15.35499 221 H 21.40604 12.98294 8.67512 222 H 21.27347 14.72206 8.86512 223 H 20.10789 14.91184 6.64448 224 H 20.14647 13.16629 6.45408 225 H 22.66295 13.20624 6.46593 226 H 22.63874 14.95693 6.66372 227 H 23.00068 14.34081 4.25459 228 H 21.47325 13.43551 4.24131 229 H 21.45608 15.19799 4.43758 230 H 17.32005 20.17569 8.47306 231 H 15.69581 20.71441 8.10199 232 H 15.70410 19.29376 5.99754 233 H 17.32813 18.74169 6.37834 234 H 18.16518 21.12124 6.26114 235 H 16.53778 21.67208 5.87266 236 H 17.90949 21.45255 3.78508 261 H 7.49015 6.78343 20.23767 262 H 8.31568 5.40430 19.51609 263 H 5.82199 5.10136 19.41779 264 H 5.66182 6.60646 18.48943 265 H 6.49086 5.20964 17.77592 266 H 14.39885 4.06424 14.83687 267 H 15.96760 4.78465 15.19443 268 H 16.52039 4.97466 12.78570 269 H 14.90265 4.46291 12.32337 270 H 15.28899 2.21314 13.34808 271 H 16.90398 2.70248 13.85586 272 H 16.99160 1.36729 11.72100 273 H 15.94996 2.56123 10.92058 274 H 17.58218 3.01863 11.44248 275 H 7.01354 15.42967 8.47242 276 H 8.05419 16.19560 7.28162 277 H 8.36253 18.17061 8.88686 278 H 7.25692 17.39953 10.01191 279 H 5.43223 17.47587 8.25925 280 H 6.54879 18.25691 7.14194 281 H 5.08403 19.96444 8.25288 282 H 5.64763 19.43218 9.85164 283 H 6.77604 20.21662 8.73135 284 H 13.07934 10.53074 4.62708 285 H 13.10405 8.87629 5.20033 286 H 15.63477 8.85410 5.05039 287 H 15.62018 10.52588 4.51241 288 H 14.28303 9.86488 2.47810 289 H 14.29779 8.18642 3.01347 290 H 16.08337 8.57795 1.29213 291 H 16.80841 9.84096 2.30848 292 H 16.82558 8.15149 2.84832 293 H 4.98661 10.07415 13.22929 294 H 5.54482 9.86955 11.57988 295 H 4.58581 12.16598 11.00128 296 H 3.98555 12.30988 12.64747 297 H 2.58137 10.23436 12.30999 298 H 3.18791 10.09854 10.66171 299 H 0.93216 11.19484 10.67970 300 H 1.54208 12.47392 11.74989 301 H 2.15487 12.33941 10.09040 302 H 7.64345 6.93133 11.04472 303 H 8.98282 6.03488 10.35783 304 H 8.90275 7.50580 8.28753 305 H 7.56056 8.40173 8.98096 306 H 6.18303 6.28440 9.04930 307 H 7.52904 5.38970 8.34994 308 H 5.86191 6.00263 6.57714 309 H 6.05181 7.72418 6.96938 310 H 7.40615 6.82196 6.26486 1 Ru 19.1127 16.9232 19.0664 2 Ru 19.1879 16.7932 14.7016 3 Ru 19.2164 15.3290 16.9275 4 Ru 17.7193 19.1054 19.0589 5 Ru 17.6543 19.1532 14.7336 6 Ru 16.4343 16.6600 19.0474 7 Ru 17.8488 17.5872 16.9033 8 Ru 16.4671 16.7561 14.8023 9 Ru 16.4334 15.0754 16.9143 10 Ru 16.3303 19.8605 16.9148 11 Ru 15.1596 17.4295 16.8879 12 Ru 12.5339 17.3545 16.8731 13 Ru 13.6707 19.5260 16.9965 14 Ru 13.6859 14.9468 17.0392 15 Ru 14.7630 21.9040 16.9339 16 Ru 15.0822 17.3693 12.7351 17 Ru 13.9047 16.5298 14.9049 18 Ru 13.7909 16.6031 18.9314 19 Ru 14.9912 17.3788 21.0523 20 Ru 16.3182 19.7714 12.7105 21 Ru 14.9403 18.9362 14.8012 22 Ru 15.0248 18.9001 18.9919 23 Ru 16.2304 19.7879 21.1693 24 Ru 16.2192 21.3079 14.8382 25 Ru 17.5470 22.1577 16.8577 26 Ru 16.1576 21.3228 19.0878 27 Ru 15.2914 12.7661 17.0101 28 Ru 16.3996 15.2356 12.6962 29 Ru 15.1517 14.4424 14.7834 30 Ru 15.2523 14.3336 19.0549 31 Ru 16.6008 15.1570 21.1077 32 Ru 17.7088 17.5663 12.6946 33 Ru 17.7000 17.5673 21.1890 34 Ru 18.8351 19.9297 12.6340 35 Ru 19.0543 19.9732 16.9426 36 Ru 18.8625 19.9363 21.1565 37 Ru 18.7996 21.4882 14.8730 38 Ru 18.5629 21.5263 19.0236 39 Ru 18.1080 12.9805 16.9082 40 Ru 16.7644 12.1383 18.7376 41 Ru 18.9843 15.3235 12.5855 42 Ru 17.8996 14.4638 14.7885 43 Ru 17.8620 14.4141 19.0270 44 Ru 19.1000 15.3543 21.0652 45 Ru 20.2942 17.7867 12.6477 46 Ru 20.5300 17.6259 16.9391 47 Ru 20.2499 17.8662 21.1517 48 Ru 20.3145 19.1266 14.7027 49 Ru 20.3999 19.1701 19.0712 50 Ru 20.5745 13.1247 17.0905 51 Ru 20.4941 14.5733 14.9009 52 Ru 21.8906 15.3563 127 C 12.4419 11.8778 22.5776 203 H 10.7583 19.0613 12.2912 279 H 14.1822 13.2428 6.3633 355 H 28.8458 15.2198 9.2903 107 C 30.9404 19.7323 13.2635 183 H 22.6100 24.2722 18.3240 259 H 12.8306 10.5648 7.0096 308 H 18.4397 18.8146 33.7003 Ru 17.8871 22.2723 17.6533 101 C 26.1657 18.2123 13.2959 177 H 7.692 27.2167 11.0506 241 H 26.1135 18.7709 14.2434 Ru 12.1330 8.0468 13.5972 Ru 17.4493 9.5733 11.3682 Ru 10.3874 10.6267 10.0131 Ru 15.4929 12.3566 7.4729 Ru 11.0313 9.6210 13.4685 Ru 16.1840 9.6585 9.2396 Ru 10.2625 11.0073 11.7021 Ru 15.1390 11.3435 7.1568 16.9023 53 Ru 20.5054 14.6998 128 C 30.1205 10.5166 22.9414 204 H 12.7779 25.1020 19.5019 280 H 16.3976 12.1120 6.8366 356 H 27.2895 14.0995 10.9460 108 C 29.6230 19.8702 12.4942 184 H 23.2614 23.0801 17.2145 260 H 15.3395 10.5039 6.8249 309 H 19.8811 17.7807 33.6773 Ru 16.5799 21.4435 19.7975 102 C 30.4297 24.4122 20.2421 178 H 7.6528 25.7747 10.0159 242 H 31.2305 24.2568 20.979 Ru 13.4927 14.8920 13.6490 Ru 18.9318 10.3363 13.5829 Ru 11.6397 17.4010 10.3155 Ru 17.1358 13.0596 9.6270 Ru 12.3867 16.4635 13.5959 Ru 15.0063 8.8653 11.3251 Ru 11.5287 17.7897 12.0531 Ru 14.1105 10.4413 9.2687 19.0020 54 Ru 21.7274 16.9939 129 C 28.7080 10.9469 22.5434 205 H 13.3956 24.4501 21.0440 281 H 17.2321 13.4422 6.0356 357 H 27.8918 15.1643 12.2133 109 C 28.3994 19.4205 13.2977 185 H 20.6584 10.5991 19.5556 261 H 15.3048 11.9794 5.8612 310 H 19.3592 20.1281 31.7383 Ru 15.5589 12.9994 17.8157 103 C 29.2383 23.4892 20.4991 179 H 6.8359 25.7579 11.5906 243 H 30.8581 24.2403 19.2427 Ru 13.4205 10.3800 9.4767 Ru 17.5195 9.5947 15.7531 Ru 11.3354 13.1717 5.9226 Ru 15.8617 12.1805 11.8028 Ru 12.3218 11.9595 9.3509 Ru 16.4205 9.6140 13.4350 Ru 11.2240 13.5673 7.6385 Ru 15.6445 11.1230 11.3019 14.7495 55 Ru 21.7141 16.8367 130 C 28.6869 12.1184 21.5578 206 H 23.8133 21.9449 18.0029 282 H 16.2502 15.0509 7.7347 358 H 27.0792 17.1664 10.8868 110 C 27.0771 19.5325 12.5338 186 H 20.1481 10.9767 21.2155 262 H 14.2464 13.2104 7.7926 311 H 20.7869 19.0971 31.7120 Ru 16.7545 15.2145 13.5536 104 C 28.097 23.6835 19.4976 180 H 9.8875 26.0089 11.1845 244 H 30.1298 25.4699 20.2943 Ru 12.1623 9.6165 11.5349 Ru 18.6583 10.2480 17.8706 Ru 10.2308 12.2861 8.0458 Ru 17.1966 12.7003 13.9009 Ru 11.0605 11.1882 11.4028 Ru 15.0190 8.7560 15.5431 Ru 10.1168 12.6852 9.7497 Ru 14.3960 10.1395 13.4719 19.1709 56 C 9.2068 14.6201 131 C 27.2762 12.5565 21.1556 207 H 23.3800 21.9920 16.2752 283 H 15.4515 13.7012 8.5362 359 H 26.4317 16.0713 9.6644 111 C 25.8706 19.0411 13.3398 187 H 18.2714 12.9647 10.3432 263 H 14.2975 11.7369 8.7566 312 H 19.3326 17.0982 31.2318 Ru 15.4963 14.5257 15.6002 105 C 26.8919 22.7787 19.7615 181 H 9.0783 25.9847 12.7487 245 H 29.5705 22.4375 20.471 Ru 13.4740 10.3610 13.6092 Ru 18.7113 11.8218 11.4858 Ru 11.6899 12.9373 10.0537 Ru 16.7359 14.6121 7.6126 Ru 12.3710 11.9338 13.4794 Ru 16.3510 9.5368 17.5427 Ru 11.5705 13.3275 11.7621 Ru 15.8445 10.8775 15.4115 16.9450 57 C 10.5892 15.2308 132 C 27.2518 13.7391 20.1828 208 H 19.6149 8.4008 18.5863 284 H 8.1465 18.5559 30.9353 360 H 24.9557 15.0121 11.4457 112 C 6.6661 7.2930 14.7920 188 H 18.1776 14.4260 9.3802 264 H 16.8130 11.7078 8.5727 313 H 17.9053 18.1314 31.2610 Ru 15.4231 14.5677 19.6434 106 C 25.7299 22.9947 18.7884 182 H 8.2344 23.6632 12.2814 246 H 28.8544 23.6568 21.5197 Ru 12.1358 9.6015 15.6252 Ru 18.7523 11.8272 15.7316 Ru 10.5314 12.0577 12.1335 Ru 17.0756 14.4526 11.8675 Ru 11.0348 11.1760 15.4963 Ru 17.5437 11.9620 9.2079 Ru 10.3930 12.4343 13.8242 Ru 16.4370 13.6853 7.1432 16.9004 58 C 18.4506 16.0507 133 C 25.8342 14.1660 19.7947 209 H 20.2724 9.4333 19.8370 285 H 9.8655 18.6772 31.3627 361 H 25.5861 16.1572 12.6256 113 C 7.4599 8.3591 15.5480 189 H 22.0549 19.8342 15.8137 265 H 16.7556 13.1856 7.6111 314 H 18.8363 19.4562 29.3209 Ru 16.6828 15.1739 21.8084 107 C 24.535 22.0864 19.085 183 H 9.0178 23.6936 10.7028 247 H 27.7725 24.7391 19.5188 Ru 13.4785 10.2768 17.7289 Ru 18.6458 5.7575 13.5047 Ru 12.0280 12.7529 14.2685 Ru 16.9214 8.4866 9.3170 Ru 12.3780 11.8433 17.5999 Ru 16.3480 11.1428 11.2401 Ru 11.8355 13.0683 15.9130 Ru 15.3838 12.7515 9.1967 25.3323 59 C 18.4880 16.2343 134 C 31.3911 14.3315 10.0142 210 H 17.7218 12.6218 8.9190 286 H 9.0434 20.0504 30.5980 362 H 27.8877 5.9392 17.3951 114 C 8.7574 8.7619 14.8428 190 H 19.3851 14.2996 15.4134 266 H 15.6489 14.3875 9.5429 315 H 20.2465 18.3981 29.2846 Ru 18.024 17.5346 13.4345 108 C 19.7964 17.8294 33.2996 184 H 11.2605 23.9764 11.8332 248 H 28.4746 23.5039 18.4752 Ru 14.7805 12.6725 9.4762 Ru 18.6975 7.2853 11.4540 Ru 12.6398 15.5015 5.9528 Ru 16.8080 10.1056 7.3483 Ru 13.6757 14.2460 9.3525 Ru 17.8320 11.9043 13.4485 Ru 12.5438 15.8913 7.6705 Ru 17.0118 13.4497 11.3659 23.8313 60 C 24.2940 17.0478 135 C 30.0563 14.1711 10.7433 211 H 18.5044 14.0424 8.2360 287 H 9.5269 17.3151 29.2469 363 H 27.1392 5.9875 19.0044 115 C 9.5512 9.8375 15.5887 191 H 17.7065 21.5411 12.5600 267 H 15.7300 12.9189 10.5012 316 H 18.7436 16.4213 28.8392 Ru 18.018 17.5581 21.978 109 C 20.0312 18.1773 31.8287 185 H 10.4706 23.891 13.4068 249 H 27.2111 21.7224 19.7183 Ru 13.4738 11.8963 11.5294 Ru 20.0843 8.0223 13.5070 Ru 11.5001 14.5706 8.0326 Ru 18.3152 10.7676 9.3775 Ru 12.3713 13.4743 11.4059 Ru 16.4193 11.1598 15.6231 Ru 11.3935 14.9653 9.7526 Ru 15.7415 12.5630 13.5437 11.1468 61 C 23.0809 17.0625 136 C 29.0312 15.2491 10.3788 212 H 22.0553 18.7683 14.9196 288 H 8.7273 18.6905 28.4908 364 H 26.4557 4.9480 17.7395 116 C 10.8598 10.2256 14.8972 192 H 14.4862 20.0959 21.7296 268 H 33.0929 20.0452 13.0388 317 H 17.3397 17.4871 28.8637 Ru 19.3162 19.6756 13.3722 110 C 19.3295 17.2176 30.8646 186 H 9.653 21.5737 12.8804 250 H 26.5335 22.9429 20.7929 Ru 14.8685 12.6670 13.6438 Ru 18.7563 7.2353 15.6060 Ru 13.0515 15.2801 10.0817 Ru 17.1472 9.8634 11.4957 Ru 13.7723 14.2368 13.5273 Ru 17.5608 11.8183 17.7369 Ru 12.9325 15.6650 11.8154 Ru 17.0498 13.0637 15.6507 12.0529 62 C 11.5481 19.7931 12.0399 63 C 12.8300 19.2531 12.6329 64 C 13.6870 24.8073 20.0443 65 C 14.3204 23.6527 19.3048 66 C 23.0054 22.1757 17.2951 67 C 21.8629 21.2226 17.5523 68 C 20.1342 9.3621 18.7454 69 C 19.1545 10.4436 18.3596 70 C 17.5986 13.7093 8.7625 71 C 17.6104 14.3305 10.1416 72 C 25.8147 15.3664 18.8258 73 C 24.3967 15.7434 18.4727 74 C 12.9858 10.7490 13.8908 75 C 13.9328 11.7197 14.5566 76 C 14.3677 19.1039 25.0615 77 C 14.7642 18.8852 23.6180 78 C 13.9371 12.1748 22.7232 79 C 14.5113 13.1990 21.7706 80 C 6.2592 25.3357 11.8816 81 C 7.6265 24.8936 12.4047 82 C 8.0383 23.5014 11.9189 83 C 9.3965 23.0409 12.4533 84 C 9.8081 21.6490 11.9668 85 C 11.1478 21.1831 12.5405 86 C 2.4323 13.6421 13.5162 87 C 3.8387 14.2307 13.3951 88 C 4.6935 14.0096 14.6458 89 C 6.1055 14.5913 14.5410 90 C 6.9577 14.3418 15.7876 91 C 8.3686 14.9270 15.6937 92 C 11.7039 4.1538 10.2646 93 C 12.7710 5.0637 10.8749 94 C 12.1908 6.3345 11.5005 95 C 13.2414 7.2591 12.1222 96 C 12.6372 8.5310 12.7212 97 C 13.6614 9.4758 13.3555 98 C 13.7663 12.0744 2.3329 99 C 13.8097 12.9151 3.6098 100 C 15.0434 12.6393 4.4737 101 C 15.0859 13.4582 5.7663 102 C 16.3286 13.1931 6.6198 137 C 27.7034 15.1073 11.1267 138 C 26.6557 16.1562 10.7425 139 C 25.3648 16.0304 11.5553 140 C 26.9253 5.9257 17.9264 141 C 26.0168 7.0704 17.4761 142 C 24.6641 7.0860 18.1929 143 C 23.7466 8.2280 17.7499 144 C 22.3947 8.2385 18.4674 145 C 21.4764 9.3775 18.0161 146 C 25.0805 29.5731 17.3381 147 C 23.9399 28.5603 17.4469 148 C 24.3975 27.1090 17.2756 149 C 23.2611 26.0920 17.4058 150 C 23.7081 24.6358 17.2482 151 C 22.5590 23.6422 17.4293 152 C 22.8869 26.9808 28.6425 153 C 22.3458 25.7458 27.9209 154 C 22.2629 25.9154 26.4013 155 C 21.7053 24.6852 25.6819 156 C 21.6225 24.8345 24.1601 157 C 21.0076 23.6092 23.4797 158 C 20.9056 23.7515 21.9603 159 C 20.1933 22.6060 21.2711 160 C 21.3311 27.7177 5.1629 161 C 21.2700 26.3407 5.8265 162 C 21.0743 26.4092 7.3435 163 C 20.9966 25.0374 8.0186 164 C 20.8600 25.1125 9.5415 165 C 20.6976 23.7441 10.2112 166 C 20.5955 23.8571 11.7329 167 C 20.1605 22.6013 12.4584 168 O 10.6569 16.5214 16.8752 169 O 11.5951 14.4489 16.8938 170 O 17.8005 17.1848 23.3330 171 O 19.2213 15.4172 23.1498 172 O 21.9375 17.3143 11.5089 173 O 23.2524 16.8552 13.2960 174 O 13.1464 19.5966 13.8184 175 O 13.5239 18.4471 11.9033 176 O 15.1659 22.9267 19.9485 177 O 13.9863 23.4585 18.0899 178 O 20.8587 21.2513 16.7630 213 H 19.3405 13.2845 14.5815 214 H 17.4410 20.6796 11.6901 215 H 14.5001 19.1541 20.7549 216 H 15.4008 21.2952 13.2760 217 H 17.5625 20.6615 22.0695 218 H 13.4748 16.5215 20.7327 219 H 22.2536 15.1843 15.0637 220 H 26.3538 15.1119 17.9024 221 H 26.3029 16.2322 19.2960 222 H 13.6603 13.2439 17.5002 223 H 12.4794 11.2779 13.0719 224 H 12.2267 10.4683 14.6386 225 H 21.9421 17.3017 20.9034 226 H 14.4445 20.1818 25.2633 227 H 15.1442 18.6158 25.6774 228 H 17.9315 13.9200 13.0475 229 H 14.1789 12.4928 23.7472 230 H 14.5117 11.2462 22.5457 231 H 19.2381 18.6607 11.4292 232 H 5.9907 26.3382 12.2441 233 H 6.2442 25.3643 10.7814 234 H 5.4677 24.6419 12.2035 235 H 8.3941 25.6250 12.0995 236 H 7.6213 24.9043 13.5080 237 H 7.2640 22.7709 12.2140 238 H 8.0562 23.4923 10.8144 239 H 10.1714 23.7719 12.1625 240 H 9.3752 23.0474 13.5571 241 H 9.0225 20.9212 12.2384 242 H 9.8547 21.6467 10.8632 243 H 11.9378 21.9054 12.2769 244 H 11.1026 21.1720 13.6399 245 H 1.8412 13.8117 12.6049 246 H 2.4696 12.5563 13.6917 247 H 1.8837 14.0925 14.3573 248 H 4.3509 13.7879 12.5237 249 H 3.7707 15.3125 13.1885 250 H 4.1809 14.4514 15.5187 251 H 4.7602 12.9263 14.8518 252 H 6.6137 14.1604 13.6603 253 H 6.0413 15.6773 14.3526 254 H 6.4472 14.7663 16.6705 289 H 10.8475 20.0426 28.7446 290 H 11.6424 18.6418 29.4592 291 H 11.2369 17.3465 27.3166 292 H 10.4799 18.7759 26.6151 293 H 12.6448 20.0568 26.9799 294 H 13.3930 18.5780 27.5776 295 H 12.9624 17.4771 25.3259 296 H 12.2287 18.9749 24.7577 297 H 20.6699 19.7027 32.7809 298 H 19.0305 19.0967 32.4686 299 H 20.3842 17.9587 32.6098 300 H 20.0585 20.0584 30.3673 301 H 21.4125 18.9409 30.5082 302 H 19.8513 16.9956 30.2510 303 H 18.4815 18.0985 30.1412 304 H 19.4445 19.1146 28.0594 305 H 20.8426 18.0472 28.1718 306 H 19.3622 16.0443 27.9232 307 H 17.9389 17.0835 27.8650 308 H 18.7637 18.1510 25.7590 309 H 20.2374 17.1767 25.8241 310 H 14.9106 32.8078 22.8925 311 H 13.3749 32.2428 22.2026 312 H 13.9348 31.6047 23.7601 313 H 15.3490 31.1519 21.0510 314 H 15.9083 30.5195 22.5977 315 H 13.7841 29.1929 22.8264 316 H 13.2186 29.8289 21.2837 317 H 15.1750 28.7565 20.1185 318 H 15.7506 28.1245 21.6607 319 H 13.6181 26.8169 21.9264 320 H 13.0303 27.4585 20.3931 321 H 14.9470 26.3547 19.1913 322 H 15.5389 25.7055 20.7262 323 H 7.1746 7.7861 25.5992 324 H 8.7036 6.9846 25.1829 325 H 8.6412 8.1233 26.5416 326 H 8.2043 8.8768 23.5776 327 H 8.1264 10.0083 24.9252 328 H 10.5289 9.5295 25.4765 329 H 10.6165 8.3937 24.1327 330 H 10.1534 10.2444 22.5086 365 H 26.5263 8.0349 17.6437 366 H 25.8488 7.0029 16.3878 367 H 24.1536 6.1210 18.0251 368 H 24.8312 7.1530 19.2828 369 H 24.2561 9.1930 17.9186 370 H 23.5801 8.1610 16.6604 371 H 21.8861 7.2723 18.3004 372 H 22.5598 8.3094 19.5570 373 H 21.9777 10.3455 18.1889 374 H 21.3065 9.3108 16.9298 375 H 24.7203 30.6040 17.4647 376 H 25.8479 29.3920 18.1060 377 H 25.5757 29.5119 16.3570 378 H 23.4428 28.6685 18.4262 379 H 23.1691 28.7882 16.6909 380 H 24.8836 26.9941 16.2905 381 H 25.1772 26.8836 18.0252 382 H 22.7757 26.2158 18.3902 383 H 22.4816 26.3157 16.6565 384 H 24.1654 24.4957 16.2527 385 H 24.5038 24.4167 17.9821 386 H 22.0980 23.7893 18.4201 387 H 21.7679 23.8419 16.6900 388 H 22.9374 26.8246 29.7295 389 H 23.9003 27.2332 28.2952 390 H 22.2485 27.8589 28.4619 391 H 22.9817 24.8743 28.1526 392 H 21.3437 25.4999 28.3117 393 H 21.6334 26.7925 26.1672 394 H 23.2674 26.1500 26.0058 395 H 22.3274 23.8060 25.9265 396 H 20.6987 24.4605 26.0772 397 H 21.0253 25.7306 23.9137 398 H 22.6324 25.0213 23.7535 399 H 21.5941 22.7099 23.7231 400 H 20.0010 23.4299 23.8907 401 H 20.3780 24.6761 21.6784 402 H 21.9083 23.8336 21.5054 403 H 16.0374 22.9060 16.0159 404 H 21.4860 27.6386 4.0775 405 H 20.3990 28.2796 5.3262 406 H 22.1552 28.3208 5.5737 1 Ru 19.1566 17.9169 20.0149 2 Ru 19.2346 17.8192 15.6802 3 Ru 19.2461 16.3489 17.8697 4 Ru 17.6631 20.0473 20.0851 5 Ru 17.6218 20.1198 15.6492 6 Ru 16.3377 17.7373 19.9706 7 Ru 17.8199 18.5805 17.8535 8 Ru 16.4518 17.7230 15.7457 9 Ru 16.4567 16.1280 17.8556 10 Ru 16.3380 20.8548 17.8380 11 Ru 15.0917 18.4356 17.7847 12 Ru 12.4530 18.5108 17.6882 13 Ru 13.6056 20.6003 17.8531 14 Ru 13.5020 16.0500 17.8150 15 Ru 14.7735 22.8662 17.7995 16 Ru 15.0931 18.3162 13.6523 17 Ru 13.8565 17.5399 15.7831 18 Ru 13.7085 17.6953 19.8238 19 Ru 15.0451 18.3425 22.0244 20 Ru 16.4357 20.8012 13.5706 21 Ru 14.9576 19.9525 15.7003 22 Ru 14.9468 19.9675 19.8770 23 Ru 16.2607 20.6630 22.0817 24 Ru 16.2176 22.2950 15.7835 25 Ru 17.4461 23.1833 17.8938 26 Ru 16.1777 22.2999 19.9944 27 Ru 15.2943 13.7988 17.9399 28 Ru 16.5281 16.1917 13.6372 29 Ru 15.1984 15.3696 15.8033 30 Ru 14.9454 15.3979 19.8274 31 Ru 16.3482 15.9929 21.8952 32 Ru 17.7163 18.4485 13.6213 33 Ru 17.6656 18.4146 22.1414 34 Ru 18.9798 20.6752 13.5900 35 Ru 18.9787 21.0511 17.9240 36 Ru 18.7891 20.7932 22.1897 37 Ru 18.8268 22.3759 15.7828 38 Ru 18.6071 22.4147 20.1910 39 Ru 17.9809 13.9846 17.9701 40 Ru 16.6194 13.7134 20.4196 41 Ru 19.0953 16.3062 13.5504 42 Ru 17.9095 15.4630 117 C 11.6372 11.3169 15.6377 193 H 15.8001 22.3888 13.9954 269 H 32.2732 19.5531 11.5434 318 H 18.2872 18.7639 26.8927 Ru 19.3767 20.1593 17.7415 111 C 19.5409 17.55 29.3846 187 H 10.3943 21.6699 11.2835 251 H 25.411 24.0513 18.8305 Ru 13.5030 11.8390 15.7212 Ru 19.9913 9.5343 11.4343 Ru 11.8341 14.3116 12.2385 Ru 18.0433 12.3584 7.3612 Ru 12.4058 13.4078 15.5958 Ru 17.6040 13.3938 11.3482 Ru 11.7083 14.6958 13.9573 Ru 16.6253 15.0073 9.3553 15.7424 43 Ru 18.0141 15.5166 118 C 30.0818 25.2994 20.3267 194 H 17.5053 21.6185 23.0710 270 H 32.0964 21.2121 12.1468 319 H 19.6777 17.6754 26.8747 Ru 19.1905 19.8825 22.0144 112 C 18.8293 16.5708 28.4472 188 H 12.6644 21.945 12.3754 252 H 26.0799 22.8242 17.7548 Ru 14.8110 12.5180 17.7700 Ru 20.0055 9.4510 15.7123 Ru 13.2551 15.0579 14.1590 Ru 18.3665 12.0849 11.6312 Ru 13.7178 14.0833 17.6454 Ru 17.6580 13.3863 15.5951 Ru 13.1100 15.3623 15.9429 Ru 16.9458 14.8278 13.6185 19.9480 44 Ru 19.0691 16.3160 119 C 28.8715 24.4020 20.5880 195 H 13.3147 18.1160 21.5078 271 H 31.0590 18.6841 13.5871 320 H 7.3773 31.5564 20.4998 Ru 19.1979 21.4242 15.557 113 C 19.0218 16.8714 26.9582 189 H 11.9147 21.777 13.9608 253 H 24.8497 21.0319 19.0328 Ru 14.7933 14.1403 11.5895 C 11.4890 17.2755 12.9176 Ru 12.8164 16.8515 8.1102 C 12.0555 14.4164 16.7555 Ru 13.6788 15.7160 11.4873 Ru 17.5433 7.3248 13.3723 Ru 12.7020 17.2455 9.8459 Ru 16.8018 8.8773 11.0391 22.1062 45 Ru 20.3357 18.6897 120 C 27.7190 24.6295 19.6060 196 H 22.2453 16.2484 15.9494 272 H 30.8823 20.3294 14.1894 321 H 7.9849 30.8987 22.0331 Ru 18.9763 21.5068 20.0099 114 C 8.5974 30.2512 20.8829 190 H 2.7569 11.9322 13.9453 254 H 24.1959 22.246 20.12 Ru 16.1325 14.9058 13.6425 C 5.4717 23.8730 14.0956 Ru 14.2822 17.5597 10.0831 C 12.5021 16.3936 25.4649 Ru 15.0345 16.4805 13.5062 Ru 17.5928 8.8575 11.3212 Ru 14.1650 17.9425 11.8342 Ru 16.6948 10.4968 9.0745 13.5716 46 Ru 20.4771 18.7002 121 C 26.5118 23.7276 19.8731 197 H 25.7429 15.3927 20.6345 273 H 29.4917 20.9213 12.1802 322 H 8.9814 32.0296 21.0964 Ru 18.2322 13.0386 17.8823 115 C 9.2309 29.0871 20.12 191 H 3.534 10.9515 15.205 255 H 20.3119 18.5315 33.9703 Ru 14.8085 14.1065 15.7152 C 6.3325 23.1253 13.0733 Ru 13.1358 16.6242 12.2181 C 11.9005 15.3395 24.5314 Ru 13.7250 15.6745 15.6044 Ru 18.9820 9.5890 13.3705 Ru 13.0020 16.9873 13.9677 Ru 18.1963 11.1575 11.1215 17.8819 47 Ru 20.3238 18.6312 122 C 25.3393 23.9453 18.9126 198 H 26.2717 16.9988 20.1665 274 H 29.6839 19.2822 11.5614 323 H 8.1680 29.1991 20.1650 Ru 16.9551 12.6511 20.1654 116 C 10.5049 28.5509 20.7796 192 H 2.6744 12.4401 15.6442 256 H 18.7247 17.8574 33.5488 Ru 13.4435 5.8255 13.5468 C 7.1993 22.0353 13.7106 Ru 11.7391 8.4378 9.7476 C 12.2178 15.6036 23.0580 Ru 12.3408 7.3975 13.4163 Ru 17.6573 8.8025 15.4705 Ru 11.6168 8.8218 11.4496 Ru 17.0123 10.2420 13.2244 22.1126 48 Ru 20.3095 20.1996 123 C 24.1584 23.0188 19.2107 199 H 13.7452 14.3969 18.6916 275 H 28.5432 18.3739 13.6192 324 H 9.1592 30.3188 19.2355 Ru 19.3141 15.3174 13.3906 117 C 11.1279 27.3697 20.0322 193 H 5.2392 12.3183 13.927 257 H 20.1614 16.8175 33.5326 Ru 14.7378 8.1170 9.4292 C 8.0850 21.2482 12.7332 Ru 12.7062 10.9274 5.6616 C 11.6465 14.5830 22.0604 Ru 13.6330 9.6933 9.3007 Ru 18.8900 11.1073 11.3017 Ru 12.6040 11.3245 7.3723 Ru 17.9328 12.7463 9.1039 15.7676 49 Ru 20.2839 20.2794 124 C 19.5066 18.7859 33.4307 200 H 12.7369 12.0463 13.9007 276 H 28.3346 20.0151 14.2261 325 H 10.9148 30.2670 21.0348 Ru 18.2126 14.4974 15.5765 118 C 12.3676 26.7855 20.7155 194 H 4.3827 13.797 14.3528 258 H 19.6847 19.2063 31.6328 Ru 13.4463 7.3368 11.4800 C 8.9043 20.1825 13.4688 Ru 11.5595 10.0408 7.7711 C 12.0415 14.9723 20.6349 Ru 12.3438 8.9113 11.3482 Ru 18.9068 11.0178 15.5771 Ru 11.4443 10.4310 9.4726 Ru 18.2348 12.4695 13.3721 20.0570 50 Ru 20.4565 14.1026 125 C 19.7092 19.1030 31.9482 201 H 13.5793 10.7877 14.8360 277 H 26.9164 20.5828 12.2324 326 H 9.9155 29.1645 21.9805 Ru 18.1314 14.6769 19.7536 119 C 12.9434 25.5805 19.9678 195 H 4.8223 13.356 16.7886 259 H 21.1141 18.1773 31.6174 Ru 14.7525 8.0083 13.5580 C 9.8295 19.2965 12.6162 Ru 12.9983 10.6402 9.7717 C 11.5895 14.1113 19.4368 Ru 13.6518 9.5798 13.4272 C 10.3722 18.7190 13.0039 Ru 12.8720 11.0233 11.4790 C 11.7448 14.5800 18.4493 17.9366 51 Ru 20.5387 15.5460 126 C 18.9837 18.1248 31.0208 202 H 22.0395 18.4051 21.7156 278 H 27.1499 18.9564 11.5942 327 H 10.0156 27.4761 20.1074 Ru 19.4152 15.3892 21.9024 120 O 11.0145 16.6884 18.0662 196 H 5.6777 11.8734 16.3685 260 H 19.6805 16.1882 31.0586 Ru 13.4835 7.2630 15.6044 C 10.5498 18.2895 13.5252 Ru 11.8986 9.7759 11.8698 C 12.1603 14.8262 18.2092 Ru 12.3810 8.8343 15.4723 C 8.8727 20.6862 12.5320 Ru 11.7608 10.1610 13.5725 C 10.7350 13.8273 20.6281 15.7313 52 Ru 21.8586 16.3146 127 C 19.1702 18.4251 29.5312 203 H 7.3598 28.1040 11.2525 279 H 26.0274 17.9963 13.6490 328 H 11.0425 28.5681 19.1822 Ru 20.6377 17.5833 13.4168 121 O 11.956 14.6206 17.9762 197 H 7.3731 13.1943 15.0782 261 H 18.2469 17.212 31.0842 Ru 14.8173 7.9473 17.7271 O 12.0045 16.3915 13.6211 Ru 13.3348 10.4274 13.9227 O 11.6591 13.2889 16.3086 Ru 13.7173 9.5143 17.5971 C 7.8790 21.5755 12.9332 Ru 13.1840 10.7837 15.6226 C 10.5473 14.0065 21.9986 17.8160 53 Ru 20.5471 15.7154 128 C 18.4163 17.4528 28.6200 204 H 7.3181 26.6875 10.1830 280 H 25.7855 19.6210 14.2726 329 H 12.7960 28.4557 20.9804 Ru 20.7974 17.7779 17.7037 122 O 18.1391 17.2267 24.1178 198 H 6.5069 14.686 15.4422 262 H 19.1853 18.5759 29.1841 Ru 16.0362 10.3878 9.3691 O 11.7878 17.3268 11.6113 Ru 13.9288 13.2497 5.6162 O 12.5010 15.3662 15.9942 Ru 14.9388 11.9680 9.2440 C 7.3480 21.4948 14.2236 Ru 13.8258 13.6488 7.3367 C 11.1463 15.0863 22.6572 19.9613 54 Ru 21.7921 18.0771 129 C 18.6064 17.7366 27.1282 205 H 6.5153 26.6284 11.7641 281 H 5.7442 7.0200 15.3252 330 H 11.7562 27.3963 21.9334 Ru 20.6633 17.6876 21.9298 123 O 18.8825 15.0931 23.8892 199 H 6.9101 14.3493 17.8906 263 H 20.6223 17.5539 29.1604 Ru 14.7870 9.6338 11.4598 H 11.3038 18.0648 11.1873 Ru 12.8512 12.3512 7.7428 H 17.1671 14.1253 15.0200 Ru 13.6878 11.2055 11.3308 C 7.8250 20.5245 15.1133 Ru 12.7368 12.7440 9.4546 C 11.9382 15.9900 21.9419 15.7882 55 Ru 21.8012 17.9522 130 C 8.2775 31.1875 21.0121 206 H 9.5623 26.9021 11.3364 282 H 6.3791 7.6465 13.7902 331 H 11.7856 25.7023 20.0506 Ru 20.644 19.2483 15.5117 124 O 22.498 18.0912 12.6238 200 H 7.7368 12.8268 17.5601 264 H 19.1856 15.5474 28.6592 Ru 16.1745 10.3220 13.6120 H 4.8590 24.6493 13.6162 Ru 14.3745 12.9905 9.7969 H 12.2642 16.1865 26.5180 Ru 15.0738 11.8943 13.4826 C 8.8170 19.6310 14.7176 Ru 14.2580 13.3793 11.5222 C 12.1240 15.8215 20.5725 20.0023 56 C 9.1557 15.7339 131 C 8.9078 30.0115 20.2651 207 H 8.7675 26.8405 12.9067 283 H 7.2587 6.3749 14.6603 332 H 12.8615 26.7470 19.1336 Ru 20.6594 19.3372 19.8425 125 O 23.702 17.5053 14.445 201 H 9.5046 14.0291 16.2691 265 H 17.7496 16.5683 28.6783 Ru 14.7915 9.5003 15.7531 H 4.7880 23.1888 14.6206 Ru 13.1911 12.0560 12.0280 H 13.5986 16.4295 25.3736 Ru 13.6900 11.0702 15.6231 C 9.3515 19.6935 13.4137 Ru 13.0735 12.4243 13.7184 C 11.5213 14.7405 19.9040 18.3258 57 C 10.5151 16.3492 132 C 10.1644 29.4609 20.9459 208 H 7.9272 24.5270 12.3970 Ru 20.7589 13.153 17.6879 126 O 13.6339 19.8594 14.4655 202 H 8.6726 15.5684 16.5211 266 H 18.6589 17.8836 26.7221 Ru 16.0680 10.2063 17.8165 H 6.0932 24.3663 14.8582 Ru 14.5832 12.7294 13.9891 H 12.1208 17.3993 25.2305 Ru 14.9705 11.7693 17.6896 O 10.8483 17.8623 13.7881 Ru 14.4343 13.0885 15.7097 O 11.3065 13.5265 17.8498 18.1004 58 C 17.8178 16.7517 133 C 10.7790 28.2674 20.2115 209 H 8.7000 24.5920 10.8144 Ru 20.8562 14.7053 15.5628 127 O 13.7652 18.4286 12.7174 203 H 20.9108 1.4112 22.1144 267 H 20.0967 16.8581 26.7124 Ru 17.3513 12.5875 9.3408 H 5.6815 22.6740 12.3058 Ru 15.2256 15.4529 5.5994 H 12.2756 14.3413 24.8136 Ru 16.2500 14.1675 9.2183 O 10.8315 18.7113 11.7369 Ru 15.1265 15.8395 7.3333 O 12.3880 15.5192 17.8422 26.2494 59 C 18.0215 16.9810 134 C 12.0148 27.6794 20.8976 210 H 10.9491 24.8542 11.9308 Ru 22.1214 15.3262 17.7134 128 O 15.483 22.968 20.6514 204 H 22.2688 2.3198 21.4207 268 H 7.6808 30.6068 20.3908 Ru 16.1600 11.8935 11.4358 H 6.9783 23.8443 12.5419 Ru 14.1842 14.6391 7.7339 H 10.8070 15.3060 24.6702 Ru 15.0520 13.4718 11.3126 H 10.3683 19.3840 11.2008 Ru 14.0740 15.0338 9.4630 H 17.0310 14.5063 16.7466 24.7702 60 C 24.5623 19.1492 135 C 12.5759 26.4628 20.1578 211 H 10.1728 24.7555 13.5097 Ru 20.7974 14.7074 19.8522 129 O 14.5051 23.6142 18.7168 205 H 21.7357 2.6519 23.08 269 H 8.3304 29.9551 21.9089 Ru 17.5540 12.7243 13.6448 H 7.8405 22.4945 14.4838 Ru 15.7318 15.4046 9.8851 H 11.8487 16.6096 22.7881 Ru 16.4532 14.2963 13.5156 H 9.1882 18.8715 15.4053 Ru 15.6125 15.7873 11.6360 H 12.7398 16.5157 20.0021 12.5568 61 C 23.3195 18.7051 136 O 10.6022 17.6267 18.0756 212 H 9.3450 22.4424 12.9636 Ru 22.0794 16.9901 15.6391 130 O 21.2328 21.3931 17.5147 206 H 20.047 3.1675 20.5456 270 H 9.289 31.1042 20.9556 Ru 16.2080 11.8330 15.7927 H 6.5443 21.3265 14.2483 Ru 14.5430 14.3664 11.9977 H 13.3148 15.6489 22.9314 Ru 15.1138 13.3935 15.6699 H 7.4148 20.4650 16.1221 Ru 14.4028 14.7475 13.7465 H 12.4128 16.8288 22.4531 13.3009 62 C 11.6109 20.8296 137 O 11.4989 15.5386 17.9204 213 H 10.0982 22.5481 11.3724 Ru 21.959 16.9225 19.7593 131 O 22.1218 20.7662 19.4918 207 H 19.5234 3.5063 22.1922 271 H 8.5005 28.265 20.029 Ru 17.4258 12.4258 17.8955 H 7.4535 20.7750 11.9613 Ru 15.8911 14.9915 14.0924 H 12.0218 13.5743 22.3042 Ru 16.3285 13.9935 17.7679 H 6.5653 22.1883 14.5343 Ru 15.7350 15.3600 15.8431 H 10.9980 15.2238 23.7294 12.9067 63 C 12.8712 20.2545 138 O 17.7009 18.1115 24.2780 214 H 12.3596 22.8133 12.4798 C 9.5991 14.7637 18.3096 132 O 18.4202 11.0365 20.4602 208 H 21.4025 5.1611 22.45 272 H 9.4612 29.4018 19.0879 Ru 17.3998 14.0950 11.5471 H 8.7565 21.9435 12.2002 Ru 15.4019 16.8577 7.8632 H 10.5484 14.5414 22.1592 Ru 16.2995 15.6720 11.4252 H 7.5203 22.3343 12.2369 Ru 15.2880 17.2485 9.6197 H 9.9313 13.3025 22.5599 13.5104 64 C 13.7809 25.8360 139 O 18.5206 16.0062 24.0840 215 H 11.5990 22.6562 14.0612 C 10.9505 15.4102 18.117 133 O 19.5839 11.4223 18.5512 209 H 21.9338 4.8129 20.8055 273 H 11.2445 29.3671 20.8624 Ru 17.3837 14.0523 15.7911 H 9.5170 20.6790 14.2410 Ru 15.6821 16.6307 12.1153 H 11.6837 16.0026 20.4574 Ru 16.2845 15.6150 15.6731 H 9.2715 20.7978 11.5193 Ru 15.5490 17.0080 13.8713 H 10.2760 12.9868 20.1076 20.8620 65 C 14.3672 24.6358 140 O 22.1963 18.9266 12.7123 216 H 2.3523 12.6910 14.0515 C 18.2847 15.8498 26.0784 134 O 19.004 14.0301 11.7698 210 H 19.6956 5.607 19.9314 274 H 10.2743 28.2461 21.816 Ru 16.2200 5.7840 13.5983 H 8.2098 19.5223 14.0163 Ru 14.5076 8.4445 9.6144 H 13.1436 15.0422 20.5976 20.1553 66 C 22.9740 23.2309 141 O 23.4311 18.1521 14.4418 217 H 3.1381 11.7835 15.3594 C 18.446 16.0867 24.5934 135 O 16.7461 14.1005 11.8382 211 H 19.201 5.9931 21.5788 275 H 10.3709 26.5734 19.9206 Ru 14.8198 5.0620 15.4775 H 9.2320 18.7708 11.8508 Ru 13.2440 7.6002 11.5352 H 11.9723 13.0826 19.5202 18.2671 67 C 21.7809 22.3387 142 O 13.2920 20.7358 14.6142 218 H 2.2376 13.2675 15.7270 C 24.8581 18.3921 12.5276 136 H 13.4484 21.4652 17.5111 212 H 21.1152 7.6311 21.7609 276 H 11.3897 27.6822 19.0058 Ru 17.2895 8.0835 9.3733 H 10.5582 19.9343 12.0838 Ru 15.2402 10.9445 5.4356 H 10.4914 14.0465 19.3897 18.5368 68 C 19.7928 10.6270 143 O 13.4523 19.2990 12.8768 219 H 4.8283 13.1303 14.0501 C 23.6023 17.9641 13.2541 137 H 16.743 18.3638 12.344 213 H 21.5912 7.2471 20.1064 277 H 13.1415 27.5681 20.808 Ru 16.1097 7.2938 11.4577 H 11.1425 18.8285 14.2844 Ru 14.2190 10.0445 7.5508 H 11.8111 15.8711 18.2168 20.2313 69 C 18.8230 11.6680 144 O 15.0791 23.8228 20.8541 220 H 3.9330 14.6073 14.3928 C 11.9217 19.957 12.7944 138 H 12.4838 17.2032 15.7871 214 H 19.3253 8.0458 19.2953 278 H 12.1079 26.4912 21.7476 Ru 17.5248 8.0453 13.5665 H 9.8132 17.7098 14.1045 Ru 15.7594 10.7301 9.5782 H 13.2530 14.9183 18.3518 19.7269 70 C 17.6477 13.8558 145 O 14.1484 24.4958 18.9058 221 H 4.3530 14.3185 16.8430 C 13.1964 19.3812 13.365 139 H 13.9626 15.1998 20.4606 215 H 18.8948 8.469 20.9552 279 H 12.1611 24.8126 19.8515 Ru 16.1223 7.1893 15.6744 Ru 14.5187 9.7581 11.7583 10.1632 71 C 17.6953 14.6979 146 O 20.8555 22.2785 17.6612 222 H 5.2063 12.8082 16.5330 C 14.1509 24.9595 20.6726 140 H 17.9568 22.8428 15.9844 216 H 12.5745 9.1525 4.356 280 H 13.2293 25.8752 18.9468 11.4199 72 C 25.7873 16.0892 147 O 21.7490 21.6923 19.6466 223 H 6.9332 14.0266 15.1956 C 14.7469 23.7664 19.9609 141 H 18.9252 22.9929 18.9806 19.7784 73 C 24.3576 16.4539 148 O 17.7643 11.8941 20.3944 224 H 6.0760 15.5474 15.4393 C 23.3611 22.309 18.1314 142 H 15.4322 16.0755 22.8985 19.4389 74 C 12.9437 11.6847 149 O 19.1265 12.2861 18.6239 225 H 6.4481 15.4039 17.9010 C 22.1575 21.4277 18.3892 143 H 16.9047 13.3361 21.8844 14.9170 75 C 13.7473 12.7453 150 O 18.8293 14.9317 11.9549 226 H 7.2226 13.8303 17.7170 C 20.4022 9.7513 20.0894 144 H 20.5275 20.8992 14.4533 15.6348 76 C 7.4025 27.0057 151 O 16.5795 15.1410 11.8886 227 H 9.0451 14.8600 16.3447 C 19.3995 10.8129 19.697 145 H 16.8028 11.8164 18.5227 11.2334 77 C 8.6916 26.4800 152 O 23.7738 17.2963 20.2122 228 H 8.2712 16.4441 16.4779 C 17.8049 12.8905 10.0462 146 H 20.524 16.2215 12.2972 11.8667 78 C 8.7906 24.9518 153 O 23.8126 15.9012 18.4234 229 H 20.6671 2.3338 22.2710 C 17.8546 13.7305 11.3 147 H 20.4568 13.8926 14.1062 11.8548 79 C 10.0877 24.4136 154 O 14.2303 12.4485 16.7872 230 H 21.9755 3.2876 21.5435 C 7.7298 26.1181 11.0588 148 H 20.9083 16.0969 22.6822 12.4636 80 C 10.1969 22.8872 12.4189 81 C 11.5055 22.3559 13.0068 82 C 2.9092 12.7960 14.9933 155 O 13.9171 13.8695 15.0566 156 H 13.0487 22.3076 17.7138 157 H 16.4266 19.2668 12.5284 158 H 12.2374 18.1780 15.8206 231 H 21.4571 3.6183 23.2078 232 H 19.7092 4.0369 20.6957 233 H 19.1954 4.3670 22.3477 234 H 21.0077 6.1009 22.5648 C 9.0104 25.6018 11.7162 C 9.1031 24.074 11.7367 C 10.3943 23.541 12.3624 C 10.5018 22.0143 12.3275 149 H 21.0374 19.4852 21.73 150 H 22.2541 13.6378 18.5515 151 H 9.7493 13.7858 18.7884 152 H 9.002 15.3976 18.981 Domain 27 -Roberto González Gómez 410 Roberto González Gómez 411 Roberto González Gómez 412 Roberto González Gómez 413 Roberto González Gómez 414 Roberto González Gómez 415 Roberto González Gómez 416 Roberto González Gómez 417 Roberto González Gómez 418 Roberto González Gómez 419 Roberto González Gómez 420 Roberto González Gómez 421 Roberto González Gómez 422 Roberto González Gómez 423 Roberto González Gómez 424 Roberto González Gómez 425 Roberto González Gómez 426 Roberto González Gómez 427 Roberto González Gómez 428 Roberto González Gómez 429 Roberto González Gómez 430 Roberto González Gómez 434

Domain 49 -Ru 55 (THF) 2 (H) 53 Domain 70 -Ru 55 (C 7 H 15 COO) 10 (H) 27 Domain 68 -Ru 55 (C 7 H 15 COO) 8 (H) 25 Roberto González Gómez 431 Structure 70, figure 4.11 (c) -Roberto González Gómez 432 Structure 71, figure 4.11 (b) -Roberto González Gómez 433 Structure 72, figure 4.11 (d) -

Structure 73, figure 4.12 (bottom right

  ) -Ru 55 (C 7 H 15 COO) 5 (C 6 H 5 COO) 8 (H) 13

	C H	12.5982 19.1147	8.9895 18.3645	12.8551 26.5292	H H	24.1422 28.9626	21.8639 13.8713	16.9193 18.2548
	C H	13.1171 20.4811	8.7140 17.2393	14.1246 26.5095	H H	18.9630 30.0497	12.4787 14.9126	9.8427 20.2396
	C H	13.8525 18.6972	9.6830 8.9289	14.8056 20.8736	H H	18.7984 28.7605	13.9482 16.4787	8.9045 21.6849
	C H	14.0757 19.6038	10.9394 6.7472	14.2173 21.6702	H H	22.7133 26.3775	18.9615 16.9956	15.5240 21.1440
	C H	24.9030 21.8592	18.0304 5.9932	10.6173 20.9268	H H	19.8860 20.6544	13.7174 14.2493	14.7642 21.1528
	C H	26.0644 23.2081	18.2371 7.4282	9.8738 19.4000	H H	18.2784 14.9083	20.8841 13.5181	12.1342 24.8467
	C H	27.3182 22.3000	18.0190 9.6169	10.4539 18.6260	H H	15.0328 13.4725	19.6231 12.1412	21.2168 26.3542
	C H	27.4088 14.2562	17.5886 9.4858	11.7820 15.7984	H H	16.2088 11.5805	21.6927 10.8269	13.6980 25.4068
	C H	26.2516 12.9435	17.3811 7.7410	12.5308 14.5867	H H	18.1350 11.1264	21.0203 10.8882	22.6646 22.9580
	C H	24.9897 12.0176	17.6033 8.2315	11.9529 12.3266	H H	13.9664 12.5762	16.9569 12.2642	21.1590 21.4581
	C H	13.2992 12.4142	25.9524 10.4552	19.7993 11.2759	H H	22.7608 19.7816	15.3537 22.0041	15.7197 21.2203
	C H	12.7095 13.7329	27.0283 12.1898	20.4604 12.4944	H H	14.1022 14.9479	13.5712 21.8151	17.5826 25.3004
	C H	13.0142 26.3061	27.2803 17.0544	21.8025 13.5690	H H	22.4651 13.4096	17.7180 22.5246	21.4893 27.1346
	C H	13.9115 28.3860	26.4514 17.4196	22.4845 12.2364	H H	7.9957 11.6344	27.5242 20.9716	10.8782 27.9363
	C H	14.5051 28.2261	25.3743 18.1870	21.8299 9.8717	H H	7.9638 11.4156	26.1429 18.7057	9.7632 26.9236
	C H	14.2027 25.9927	25.1189 18.5753	20.4807 8.8391	H H	7.1740 12.9629	26.0217 18.0072	11.3470 25.0913
	C H	26.9562 23.9205	16.3180 18.2055	20.5169 10.1802	H H	10.2144 13.9830	26.3459 20.2044	10.9087 19.1414
	C H	28.2864 15.2060	16.0240 24.7197	20.8139 22.3473	H H	9.4298 21.3127	26.2258 25.3373	12.4811 13.9654
	C H	29.0099 14.1493	15.1444 26.6470	20.0021 23.5311	H H	8.6012 22.0342	23.9231 27.3366	11.8917 12.6580
	C H	28.4000 12.5524	14.5592 28.1241	18.8874 22.3175	H H	9.3889 22.5536	24.0433 27.1128	10.3194 10.2324
	C H	27.0707 12.0109	14.8498 27.6755	18.5842 19.9282	H H	11.6255 22.3715	24.2748 24.8908	11.4574 9.1208
	C H	26.3396 13.0737	15.7306 25.7463	19.3991 18.7533	H H	10.8383 21.6464	24.1548 22.8973	13.0297 10.4382
	Ru C H	19.6254 14.6872 26.5807	17.2457 13.7774 14.3994	19.6813 22.1592 17.7214	Ru H	22.2350 10.0036	17.1619 21.8532	19.7962 12.4370
	Ru C	19.7904 12.7594	17.1233 12.2285	15.2828 22.5319	C H	9.6949 10.7910	15.2184 21.9738	17.6615 10.8638
	Ru C	19.7643 11.9551	15.6826 11.4628	17.4689 23.3744	C H	11.0846 13.0300	15.7838 22.2001	17.4844 12.0087
	Ru C	18.2783 12.2100	19.4740 11.4290	19.6132 24.7496	C H	18.5960 12.2414	16.3578 22.0652	25.8906 13.5798
	Ru C	18.3309 13.2722	19.5052 12.1672	15.2543 25.2820	C H	18.7615 2.9720	16.5927 11.8493	24.4064 13.5291
	Ru C	16.9298 14.0783	17.0562 12.9374	19.5531 24.4449	C H	23.7623 3.6462	17.4295 11.1492	12.7709 15.0150
	Ru C	18.4113 13.8274	17.9388 12.9714	17.4654 23.0629	C H	12.2469 2.8247	20.2281 12.7205	12.4403 15.0693
	Ru C	17.0392 14.9071	17.1410 19.4770	15.3032 23.9396	C H	13.4952 5.4678	19.6505 12.1533	13.0660 13.5742
	Ru C	16.9328 13.0577	15.5213 18.9883	17.4115 25.5561	C H	14.8442 4.6518	23.9837 13.7137	19.7793 13.6175
	Ru C	16.9713 12.1951	20.2069 19.3859	17.4554 26.5772	C H	23.8047 4.9439	22.2253 13.8076	17.9067 16.1091
	Ru C	15.7113 12.3181	17.8939 20.6580	17.3650 27.1456	C H	22.5507 5.7394	21.4469 12.2356	18.2375 16.0811
	Ru C	13.1044 13.3138	17.8454 21.5309	17.3517 26.6944	C H	19.8966 7.5724	10.7066 13.1738	19.2230 14.6432
	Ru C	14.3261 14.1781	20.0313 21.1397	17.3497 25.6726	C H	18.2915 6.7757	13.3366 14.7472	9.6707 14.6409
	Ru C	14.1511 14.0521	15.3310 19.8660	17.4197 25.0928	C H	18.2808 7.0206	14.1486 14.8947	10.9447 17.1305
	Ru C	15.5232 20.9454	22.3797 22.8206	17.4173 13.0358	C H	24.9156 7.7718	16.0191 13.3001	19.0939 17.1643
	Ru C	15.7413 21.7453	17.7221 23.8728	13.1960 10.9137	C H	14.8243 9.6803	11.9849 14.1446	14.9591 15.7775
	Ru C	14.4880 22.1465	16.9527 24.9899	15.3889 10.1838	C H	8.0523 8.9298	26.4278 15.7453	10.8226 15.7005
	Ru C	14.3040 22.2500	17.0308 26.2374	19.3542 10.8087	C H	9.3517 13.2406	25.8976 9.1789	11.4304 4.0957
	Ru C	15.4530 21.9576	17.8552 26.3634	21.5162 12.1709	C H	9.4660 14.7163	24.3721 10.0179	11.3712 3.5754
	Ru C	17.0660 21.5566	20.1179 25.2498	13.1784 12.9070	C H	10.7609 14.8336	23.8270 8.5457	11.9782 4.5586
	Ru C	15.6075 21.4443	19.3568 23.9964	15.2024 12.2813	C H	10.8682 13.6101	22.3014 11.2159	11.9158 5.5146
	Ru O	15.5262 20.7985	19.3802 21.7112	19.4509 12.4216	C H	12.1620 13.7299	21.7583 9.7549	12.5257 6.4905
	Ru O	16.7618 20.6462	20.1915 22.9881	21.7091 14.2842	C H	3.4954 16.2405	12.0907 9.8488	14.4651 6.3218
	Ru O	16.8782 14.7521	21.6388 18.3077	15.3405 23.4373	C H	4.8274 16.1183	12.7951 11.3132	14.2029 5.3477
	Ru O	18.1198 15.7103	22.5076 20.3698	17.3165 23.4712	C H	5.5798 14.9647	13.1530 12.4843	15.4869 7.2613
	Ru O	16.8156 14.4488	21.7634 13.7709	19.5835 20.9084	C H	6.9283 15.1001	13.8369 11.0216	15.2471 8.2349
	Ru O	15.8226 15.6571	13.1906 14.4500	17.4812 22.6960	C H	7.6533 17.6125	14.2057 11.1520	16.5435 8.0774
	Ru O	17.0521 11.1997	15.6014 17.0646	13.1798 17.3888	C H	9.0279 17.4727	14.8430 12.6200	16.3258 7.1093
	Ru O	15.7026 12.0569	14.8349 14.9567	15.2728 17.4328	C H	14.2536 16.2755	9.4691 13.7579	4.4097 9.0251
	Ru O	15.6876 18.1212	14.7895 17.5571	19.4900 23.8735	C H	14.2279 16.4277	10.3170 12.2959	5.6820 9.9869
	Ru O	16.9751 19.5454	15.5447 15.7887	21.6137 23.7663	C H	15.6195 31.6346	10.7468 24.5492	6.1543 20.5533
	Ru O	18.3850 22.6220	17.8720 17.6637	13.2248 12.1965	C H	15.5946 31.2098	11.5928 24.4309	7.4291 18.8337
	Ru O	18.1275 23.8817	17.9021 17.0837	21.7289 13.9908	C H	16.9781 30.4882	12.0402 25.7018	7.9089 19.8392
	Ru O	19.6090 13.8112	20.1509 20.0294	13.1718 14.2451	C H	16.9161 30.0031	12.8771 22.6733	9.1886 20.2073
	Ru O	19.7095 14.1676	20.3047 18.7934	17.4754 12.3837	C H	30.8084 29.2835	24.6485 23.9395	19.8349 21.1979
	Ru O	19.3783 15.7094	20.2350 23.2852	21.7151 20.4223	C H	29.6455 28.1289	23.7168 24.8683	20.1794 19.1553
	Ru O	19.4485 14.5135	21.8190 23.7472	15.4211 18.5535	C H	28.4758 28.8345	23.8204 23.5814	19.1968 18.1794
	Ru O	19.2127 21.5257	21.7884 21.6214	19.5693 17.4960	C H	27.2949 27.6428	22.9112 21.8648	19.5459 19.6043
	Ru O	18.5625 22.5699	13.4341 20.6464	17.3178 19.2400	C H	26.1363 26.9274	23.0022 23.1641	18.5494 20.5559
	Ru O	17.3759 18.6830	12.5231 10.9862	19.1638 19.5538	C H	24.9346 25.8133	22.1338 24.0553	18.9322 18.4628
	Ru O	19.6039 20.6722	15.5956 11.4339	13.1807 18.5018	C H	20.3480 26.4958	18.2076 22.7131	33.0897 17.5461
	Ru O	18.4133 19.4119	14.8714 14.5014	15.2357 11.4392	C H	20.5715 25.2478	18.5514 21.0836	31.6161 19.0387
	Ru O	18.3069 17.1524	14.8067 14.4442	19.5307 11.4785	C H	19.7878 24.5578	17.6454 22.4377	30.6633 19.9220
	Ru O	19.4522 24.2810	15.6776 16.8302	21.6783 19.8627	C H	20.0009 20.9201	17.9655 18.8716	29.1811 33.7533
	Ru O	20.9365 24.3820	18.0890 15.4264	13.2412 18.0870	C H	19.2068 19.2856	17.0444 18.2985	28.2522 33.3624
	Ru O	21.1035 15.2800	17.9364 11.7082	17.5476 16.1241	C H	19.4116 20.6559	17.3296 17.1735	26.7620 33.3071
	Ru O	20.7148 14.9687	18.1593 13.1329	21.7662 14.3945	C H	21.7177 20.2875	8.9804 19.6017	19.2912 31.4336
	Ru H	20.9763 9.7735	19.3914 14.3225	15.3568 18.2943	C H	22.2206 21.6469	7.7560 18.4829	19.7278 31.3793
	Ru H	20.9176 9.0818	19.5265 15.9656	19.7273 18.1854	C H	21.4626 20.0682	6.9502 16.5935	20.5838 30.8515
	Ru H	20.9309 18.8939	13.3649 15.3224	17.8265 26.1075	C H	20.1955 18.7111	7.3720 17.7165	20.9998 30.8999
	Ru H	21.0100 17.5270	14.8208 16.4712	15.5189 26.1268	C H	19.6840 19.7185	8.5914 19.0151	20.5591 28.9878
	Ru H	22.3970 12.1987	15.5898 19.8840	17.5731 11.3982	C H	20.4425 21.0761	9.4062 17.8902	19.7013 28.9413
	Ru H	20.9807 11.3863	15.0460 19.7830	19.6464 12.9701	C H	13.5568 19.4837	11.2109 15.9957	12.9398 28.4604
	Ru H	22.3196 23.4986	17.2094 23.2709	15.4204 17.7405	C H	12.8207 18.1317	10.2381 17.1269	12.2648 28.4908
	Roberto González Gómez Roberto González Gómez					435 436

Structure 74, figure 4.12 (top right)-

  Ru 55 (C 7 H 15 COO) 3 (C 6 H 5 COO)(H) 11

	Ru H	20.9264 19.9974	14.9777 16.7095	15.5426 30.8650	C H	13.7644 12.1874	21.6857 27.9283	25.2338 20.0346
	Ru H	22.3144 18.5981	15.6855 17.7808	17.5961 30.8916	C H	13.6481 13.2048	20.3713 25.9969	24.7493 18.8254
	Ru H	20.8960 19.5652	15.0903 19.0940	19.6367 28.9707	C H	20.8426 26.4513	22.9960 14.3676	13.1222 17.8484
	Ru H	22.2335 20.9684	17.3302 18.0260	15.3973 28.9470	C H	21.4943 28.8092	24.1077 13.7950	10.9822 18.4341
	Ru H	22.1946 19.4662	17.3654 16.0633	19.6747 28.4653	C H	21.8019 29.9205	25.2514 14.9260	10.2481 20.3549
	C H	18.5774 18.0635	16.3717 17.1308	25.8895 28.4850	C H	21.8880 28.6811	26.4932 16.6300	10.8868 21.6829
	C H	18.7286 18.9924	16.6180 18.4040	24.4058 26.5220	C H	21.6777 26.3223	26.5865 17.1944	12.2666 21.0898
	C H	23.7340 20.4129	17.6668 17.3481	12.8195 26.5133	C H	21.3728 20.8795	25.4454 14.5967	13.0074 21.3360
	C H	12.1825 18.7856	20.4670 9.1600	12.4785 20.9790	C H	21.2722 14.9062	24.1987 13.5267	12.3673 24.8666
	C H	13.4305 19.7579	19.8856 7.0136	13.0990 21.7939	O H	20.6613 13.4459	21.9070 12.1766	12.4816 26.3741
	C H	14.9357 21.8986	24.1752 6.1761	19.8236 20.8343	O H	20.6182 11.4524	23.1247 11.0046	14.3901 25.4489
	C H	19.8098 23.0729	10.8234 7.4942	19.1044 19.0763	O H	14.4523 10.9227	18.6745 11.1787	23.2823 23.0210
	C H	18.2752 22.1105	13.4390 9.6576	9.7553 18.2945	O H	15.4439 12.3994	20.7060 12.5192	23.2299 21.5186
	C H	18.2567 14.0200	14.2591 9.7119	11.0236 15.7677	O H	14.3767 20.1856	13.8762 21.8311	20.9456 21.0239
	C H	24.8373 12.6146	16.1340 8.0160	19.1024 14.5925	O H	15.6004 14.5667	14.5467 22.3187	22.7210 24.8554
	C H	14.6208 11.6119	12.2037 8.5562	14.9299 12.3766	O H	18.0535 12.9453	17.5694 23.1887	23.8853 26.5427
	C H	7.9420 12.0345	26.6168 10.7763	10.8255 11.3281	O H	19.5308 11.1060	15.8445 21.7243	23.7558 27.3657
	C H	9.2463 13.4483	26.1057 12.4611	11.4384 12.5094	O H	22.6047 10.8997	17.9272 19.3912	12.2394 26.5180
	C H	9.3781 26.2556	24.5814 17.2984	11.3896 13.6816	O H	23.8262 12.5284	17.2477 18.5312	14.0202 24.8315
	C H	10.6753 28.3696	24.0539 17.7672	12.0073 12.4388	O H	13.7715 12.5483	20.2740 19.7501	14.2642 17.4512
	C H	10.7977 28.2701	22.5295 18.6385	11.9503 10.1071	O H	14.0782 21.1918	19.0022 25.5071	12.4198 14.0800
	C H	12.0892 26.0648	21.9956 19.0269	12.5733 9.0170	O H	15.7936 21.7410	23.4525 27.5549	20.4478 12.7647
	C H	14.1382 23.9573	9.7155 18.5582	4.4569 10.2705	O H	14.5764 22.1136	23.9415 27.3899	18.6035 10.3073
	C H	14.1421 15.3368	10.5523 24.8757	5.7363 22.3919	O H	18.6095 21.9639	11.0986 25.1774	19.4819 9.1717
	C H	15.5479 14.3221	10.9360 26.8039	6.2072 23.6105	O H	20.5420 21.4054	11.5419 23.1366	18.3290 10.4962
	C H	15.5496 12.7454	11.7745 28.3280	7.4872 22.4285	O	19.3859	14.5789	11.5510
	C	16.9442	12.1787	7.9732	O	17.1262	14.5961	11.5222
	C	16.8947	13.0155	9.2535	O	24.2196	17.0032	19.8233
	C	20.2036	18.3637	33.0840	O	24.2885	15.5129	18.1212
	C	20.4218	18.6949	31.6068	O	15.0712	11.9146	16.0974
	C	19.6784	17.7475	30.6619	O	14.8152	13.3367	14.3562
	C	19.8892	18.0591	29.1778	H	18.9303	15.3535	26.1045
	C	19.1420	17.0972	28.2513	H	17.5038	16.4269	26.1274
	C	19.3391	17.3860	26.7607	H	12.1331	20.1291	11.4341
	C	21.6025	9.0693	19.0576	H	11.3247	20.0142	13.0064
	C	22.1366	7.8603	19.5000	H	18.9197	12.5642	9.9439
	C	21.4755	7.1190	20.4846	H	18.8109	14.0322	8.9940
	C	20.2721	7.5878	21.0218	H	22.6579	19.0992	15.5673
	C	19.7251	8.7882	20.5717	H	18.2329	20.9151	12.1409
	C	20.3891	9.5399	19.5873	H	16.1617	21.8749	13.7743
	C	13.2613	11.4832	12.9526	H	18.1765	21.2079	22.6404
	C	12.4722	10.5382	12.2987	H	13.8215	17.1920	21.1596
	C	12.2358	9.2914	12.8873	H	22.6893	15.4700	15.7351
	C	12.7963	8.9885	14.1327	H	13.9291	13.8374	17.6199
	C	13.5835	9.9301	14.7933	H	22.3238	18.6955	20.8750
	C	13.8188	11.1856	14.2080	H	7.8730	27.7129	10.8727
	C	24.9287	18.3814	10.7313	H	7.8575	26.3228	9.7683
	C	26.1093	18.6433	10.0372	H	7.0676	26.2050	11.3523
	C	27.3477	18.4243	10.6494	H	10.1047	26.5601	10.9151
	C	27.4044	17.9355	11.9589	H	9.3192	26.4417	12.4868
	Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru C C C C C C C C C C C C C C C C C C C C C C C C C C	19.5789 19.6997 19.6292 18.1799 18.2667 16.8289 18.2862 16.9691 16.8521 16.8979 15.6192 13.0546 14.3188 14.2796 15.4708 15.6580 14.3501 14.2052 15.3687 17.0032 15.5175 15.5338 16.7468 16.8777 18.1323 26.2282 24.9815 13.4415 12.8763 13.1909 14.0763 14.6465 14.3313 26.8786 28.1953 28.8911 28.2671 26.9506 26.2468 14.6149 12.6156 11.7963 12.0934 13.2122 14.0321 13.7401 14.5764 12.6138 11.7067 11.8228 12.8547	17.3288 17.3314 15.8093 19.5714 19.6278 17.1385 18.0359 17.2902 15.6373 20.3553 18.0361 18.0322 20.2710 15.5433 22.4891 17.9626 17.1542 17.1945 18.0187 20.2990 19.5523 19.4656 20.2686 21.8223 22.6310 17.6705 17.8957 26.1832 27.2602 27.4849 26.6291 25.5517 25.3216 16.4541 16.1337 15.1771 14.5415 14.8572 15.8154 13.8858 12.4377 11.6903 11.5938 12.2529 13.0080 13.1026 19.8798 19.5453 20.0324 21.3427 22.1660	19.6910 15.3174 17.4669 19.6476 15.2887 19.5848 17.5052 15.3191 17.4184 17.4584 17.3886 17.3678 17.4807 17.4469 17.4858 13.2210 15.4136 19.3946 21.5465 13.2612 15.2807 19.5575 21.7204 15.4136 17.4338 12.6578 12.0485 19.8725 20.5533 21.8978 22.5622 21.8879 20.5369 20.5151 20.8414 20.0952 19.0164 18.6842 19.4342 22.1973 22.5837 23.4274 24.7911 25.3112 24.4738 23.1026 23.7042 25.2212 26.1606 26.6369 26.1736	Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H Ru H H	16.7411 8.5155 15.6998 9.3105 16.9567 11.5383 15.6116 10.7420 15.6329 9.9320 16.9271 10.7336 18.2949 12.9595 18.0634 12.1546 19.5782 13.1162 19.6577 14.6138 19.3330 14.6914 19.4682 13.5513 19.3235 13.6304 18.4433 16.1413 17.2903 16.0616 19.5679 14.9470 18.3295 15.0368 18.2522 17.5511 19.4192 17.4602 20.8653 16.2800 21.0635 16.3807 20.6676 20.7475 20.9547 19.1376 20.8238 20.5486 20.8510 20.0999 21.5003	21.8283 24.1260 13.3433 24.2449 15.7703 24.5091 15.0021 24.3866 14.8199 22.0745 15.6264 22.1992 18.0046 22.4465 17.9644 22.2967 20.2704 9.4578 20.3125 10.2578 20.2825 8.7741 21.9221 11.4708 21.7817 9.9987 13.5555 10.0183 12.6353 11.4922 15.7145 12.6856 15.0642 11.2139 14.9101 11.2720 15.7317 12.7451 18.2315 13.9134 18.0530 12.4477 18.2063 19.0576 19.5657 18.4191 19.6281 17.3449 13.5003 19.7313 18.6638	11.9080 19.6220 10.3394 17.4548 11.4899 13.2036 13.0580 15.2705 12.4638 19.5368 10.8984 21.6386 12.0684 13.2798 13.6299 21.7635 4.1442 13.2186 3.6257 17.4873 4.5954 21.7249 5.5792 15.5402 6.5420 19.4845 6.3675 17.3017 5.4027 19.1562 7.3242 13.2437 8.2888 15.2632 8.1441 19.5562 7.1778 21.6574 9.0837 13.2564 10.0453 17.5695 33.7406 21.7753 33.3508 15.4261 33.3179 19.7189 31.4087 17.7376 31.3763
	Roberto González Gómez Roberto González Gómez					437 438

Domain 75, figure 4.18 (bottom) -

  Ru 55 (CF 3 COO)(H)

	Ru C	16.7689 21.0883	13.6081 18.0948	12.3306 8.7935	Ru H	17.9954 12.4144	12.6246 6.0729	14.3338 22.0214
	Ru C	15.5008 22.2301	12.7247 17.6555	14.5100 9.4893	C H	11.4729 13.4597	14.8243 5.5896	19.3714 20.6767
	Ru C	16.8191 22.2229	13.2240 16.3875	16.6113 10.0448	C H	11.1274 7.0386	14.9746 14.0972	20.8764 11.5933
	Ru C	16.3769 19.5894	15.1655 12.3496	10.3176 10.7317	O H	11.0538 5.7973	13.7567 19.9578	18.8201 20.5130
	Ru C	16.7090 20.9884	14.9884 14.2193	14.5782 10.4522	O H	12.1521 4.3501	15.7553 19.0778	18.8367 19.9666
	Ru C	16.5548 22.0138	9.0361 13.5555	12.0082 11.1541	F H	9.7948 4.9755	14.8540 20.4071	21.0765 18.9699
	Ru C	16.4437 21.8108	10.6542 12.2776	10.0404 11.6484	F H	11.7467 4.1797	13.9966 10.5961	21.5859 16.7008
	Ru C	17.9513 20.5652	11.3160 11.6607	12.0791 11.4363	F H	11.5231 16.8507	16.1622 16.2532	21.3680 4.5576
	Ru C	16.7702 17.8139	10.4026 16.4078	14.1915 11.6877	H H	16.8026 15.1369	14.6629 17.8772	17.7093 5.3239
	Ru C	17.6838 16.4530	12.9045 14.5500	10.0679 11.3315	H	14.7484	18.1475	7.8166
	C	15.6842	14.8812	12.4498	H	16.1284	16.8129	9.3902
	C	15.9617	16.0193	13.1948	H	18.2499	14.7672	4.0628
	C	17.0761	16.7879	12.8023	H	19.9700	13.0240	3.6582
	C	16.5107	12.3165	8.4555	H	21.0905	11.9373	5.6590
	C	16.1228	13.4311	10.4686	H	20.4021	12.6407	7.9397
	C	15.0700	12.5643	10.7511	H	19.0901	17.5532	8.1766
	C	14.6792	11.5829	9.8501	H	21.0452	19.0786	8.3288
	C	15.4446	11.4537	8.6736	H	23.1043	18.2983	9.5904
	C	13.4969	10.7055	10.1332	H	23.0942	16.0258	10.5890
	C	15.0675	16.4367	14.3416	H	22.9698	14.0540	11.3087
	O	5.8629	18.4005	17.6395	H	22.6027	11.7639	12.1929
	O	7.0187	17.9599	19.5401	H	20.3503	10.6611	11.8110
	O	12.3968	7.7577	19.8152	H	18.6151	11.9021	10.5398
	O	10.5062	6.4331	19.7660	H	18.6734	16.9908	11.3572
	O	14.0663	15.6276	14.5991	H	17.3405	17.6813	13.3676
	O	15.3105	17.4827	14.9532	H	14.8228	14.2752	12.7357
	O	12.7008	11.1635	11.1053	H	14.5478	12.6568	11.7101
	O	13.2945	9.6616	9.5171	H	17.1197	12.2368	7.5558
	H	11.8960	4.7365	20.9574	H	15.1952	10.6846	7.9430
	Ru	11.1802	12.0506	18.9050	Ru	9.0161	7.4219	18.6825
	Ru	11.2141	11.9741	14.5236	Ru	11.1873	10.4695	12.4843
	Ru	11.3133	10.4882	16.7360	Ru	10.0140	9.6084	14.5699
	Ru	9.7191	14.2452	18.8471	Ru	9.9134	9.6491	18.8200
	Ru	9.8698	14.2003	14.5539	Ru	11.0399	10.5662	20.9333
	Ru	8.4347	11.8275	18.8309	Ru	12.3335	12.8310	12.4447
	Ru	9.8459	12.6975	16.7154	Ru	12.5672	12.8736	16.7301
	Ru	8.5673	11.8494	14.5652	Ru	12.2340	12.9149	21.0001
	Ru	8.6201	10.2736	16.6874	Ru	12.5073	14.3492	14.4935
	Ru	8.4280	14.9787	16.6197	Ru	12.2876	14.3526	18.8171
	Ru	7.1178	12.4734	16.6333	Ru	12.6062	8.2806	16.7051
	Ru	4.5965	12.4591	16.4841	Ru	12.5916	9.7509	14.6785
	Ru	5.8120	14.7229	16.5873	Ru	13.8600	10.5795	16.7850
	Ru	5.8640	10.1525	16.7069	Ru	12.5061	9.6788	18.8820
	Ru	6.8242	16.9757	16.5131	Ru	13.7793	12.0211	14.7098
	Ru	7.1887	12.5095	12.4685	Ru	13.6513	12.0414	18.8683
	Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru	8.7884 10.0979 10.0214 11.2879 10.9729 9.8695 11.3292 10.1559 11.6096 12.2903 11.1454 12.6917 11.4728 12.8904 12.4559 13.9262 12.7706 11.3700 12.3513 11.1951 12.6261 11.5219 5.9599 5.8312 7.0570 8.4136 7.1054 7.0545 8.2924 8.2851 9.5454 8.2124 7.3818 8.6300 7.3523 7.3037 8.5029 9.7581 9.6738 10.9377 11.0800 10.8466 10.8342 10.7658 10.1573	13.5507 15.7412 11.1708 17.9542 13.7268 12.8461 13.4936 12.6050 13.2491 16.0525 15.1275 15.8282 14.8659 15.5584 17.4067 18.1084 17.1596 8.9847 11.4846 10.5924 11.1849 10.3246 11.6463 11.7859 12.6011 14.8929 14.0174 14.0782 14.8794 16.3696 17.2840 16.4648 7.9990 10.3204 9.5020 9.4809 10.3489 12.6473 12.6842 14.9139 15.1610 15.0113 16.5478 16.5092 8.1527	12.8993 12.9638 12.6830 13.0264 8.6141 10.7270 12.7348 14.8004 16.8791 8.6424 10.7244 12.7838 14.9264 16.8998 10.8167 12.7940 14.9299 12.4279 8.3456 10.4485 12.4519 14.5496 14.5246 18.7031 20.7728 12.4830 14.5556 18.6829 20.8091 14.5257 16.5801 18.7131 16.7421 12.5517 14.6491 18.7074 20.8595 12.4907 20.8972 12.4138 16.6551 20.9328 14.5221 18.7679 16.7129	Ru Ru Ru N Ru N Ru N Ru N Ru N Ru N Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C Ru C C	12.9481 18.3955 13.5751 19.7735 12.4894 17.5121 14.0163 17.2104 12.8343 19.0134 14.2037 19.9678 14.8748 16.8626 13.8263 12.4133 15.3719 11.7123 14.1680 5.2687 15.5081 6.1162 15.0456 17.4130 15.3184 18.4053 14.1380 16.2610 12.8765 15.4978 14.8833 15.7139 13.8610 16.6711 15.4007 18.7472 14.1521 19.9500 15.6022 19.7048 16.1833 20.3255 15.1352 19.9950 21.0924	10.9535 14.6857 13.8099 13.5951 12.9050 15.3215 13.5404 15.8331 12.5897 14.0413 13.2559 16.0070 16.0043 13.3067 15.1950 5.7008 15.9476 6.7164 14.9131 19.5831 15.5235 18.5871 17.4087 15.6508 17.1705 14.6563 8.9957 16.7133 8.1510 17.4594 11.5021 17.3026 10.6013 16.3968 11.2834 14.2845 10.3033 13.0930 11.0402 13.3114 13.8453 12.7024 12.9095 17.2481 15.5572	9.1532 16.5984 10.2331 8.3086 10.9287 10.4275 7.9161 12.4919 7.3003 14.6927 9.2427 16.6795 9.3199 8.3031 20.9858 10.4336 20.1076 12.5996 19.6303 14.7169 18.8863 16.8107 6.5593 10.5850 6.2186 14.8313 8.3137 12.2964 7.4288 14.2198 6.0479 8.1238 5.6223 10.2387 4.9030 12.2703 7.0581 14.4416 4.6755 16.3795 5.7822 8.1066 8.7004 10.1628 9.9132
	Roberto González Gómez Roberto González Gómez					439 440

Domain 76, figure 5.4 (left) -Ru 55 (CH 3 COO) 2 (PS1)(H) 2

Domain 77, figure 5.4 (right) -

  Ru 55 (CH 3 COO) 2 (PS2)(H) 2 Domain 79, figure 5.5 (right) -Ru 55 (CH 3 COO) 2 (PS4)(H) 2 Ru 55 (CH 3 COO) 10 (PS2)(H) 27 Ru 55 (CH 3 COO) 10 (PS4)(H) 27 Ru 55 (CH 3 COO) 14 (PS4)(H) 31

	Ru Ru H C H C C C	16.5872 11.6596 18.2218 13.3617 22.0835 14.0203 15.0613 8.4373	12.9018 8.6144 10.3320 16.2011 14.4004 15.4987 15.0731 10.2055	12.3643 11.5609 10.1853 22.2211 17.7787 22.6382 5.2087 11.4296	C C H H H H H	10.4332 15.5736 21.2864 8.0432 18.2366 8.1570 9.7187	11.8600 18.5538 17.4585 17.5393 10.3438 20.9123 14.4927	12.1742 13.3341 6.1751 11.5039 14.6971 13.1577 17.0393
	Ru Ru H C C C C	15.5205 10.1042 20.6342 13.6115 14.1529 14.7662 9.4273	12.2048 12.3636 10.4934 16.3038 15.5622 15.4667 11.1728	14.5163 13.7293 10.7627 20.7367 21.1369 6.6338 12.0287	C C H H H H H	10.2843 14.6114 20.8292 9.1972 15.8145 12.6387 15.0835	11.8369 17.0222 18.9596 15.3376 9.6055 19.1188 21.7344	13.5968 14.8343 10.1964 16.3879 14.6625 8.3351 13.2329
	Ru Ru H C C C C	15.5398 10.0261 21.8069 20.5636 20.6289 9.4722 9.9489	12.7895 12.3517 12.7190 17.5061 16.4777 11.1057 19.0127	18.7450 9.3831 10.4490 8.6103 8.6207 8.8819 22.0304	C C H H H H H	14.8506 13.3253 22.0337 14.2124 17.8924 8.0577 14.3035	7.8627 17.3351 19.0089 23.1462 12.4987 17.1231 22.2969	11.1329 14.4106 7.9607 12.4252 22.2490 10.6537 15.4047
	Ru Ru H C C C C	16.6808 8.8300 20.4886 19.2479 19.3698 10.1174 10.5942	14.0110 9.9884 14.6570 17.3747 16.3945 12.0747 18.6544	20.6767 13.7759 9.6197 9.3350 9.4486 9.8405 20.7157	C C H H H H H	11.0658 13.1623 16.8428 14.5845 9.2268 8.9983 12.2582	10.8058 18.3083 13.2982 22.9875 20.7116 14.2948 12.9057	14.3002 13.4103 6.3847 15.0049 13.9452 15.3027 11.0052
	Ru Ru H C C C C	17.7458 10.1895 18.0825 7.5630 7.6451 8.0925 10.1487	15.3375 10.8284 14.4819 20.0264 19.1476 17.8689 11.1573	12.1728 11.5936 11.7778 8.6826 9.3037 21.1491 19.9288	C C H H H H H	10.8605 14.2899 17.6613 12.2493 12.5143 13.3850 11.0894	10.5233 18.9125 12.9674 13.4116 17.6441 23.3519 15.3072	15.7293 12.8778 4.0633 11.1889 8.8329 13.3801 19.1673
	Ru Ru H C C C C	17.8360 8.7974 17.4012 8.8344 8.9558 8.7680 10.7542	15.8886 9.9434 15.4008 19.4725 18.6340 17.8755 12.1925	16.2300 9.4834 13.9771 9.2679 9.8347 19.8014 19.0123	C C H H H H H	16.5420 16.8108 19.5396 10.3505 8.3673 13.1407 13.8560	15.6111 19.1011 14.4490 16.0176 16.7368 22.8793 13.3673	9.9614 12.8197 3.2111 18.4761 11.9415 15.8252 18.0455
	Ru Ru H C C C C	17.6126 8.9132 16.4143 9.8294 10.1195 9.9497 15.8282	16.4712 8.4123 17.4004 25.2030 24.4240 10.3504 23.1341	20.4541 11.6485 15.2031 16.4837 16.8920 17.6181 8.3368	C C H H H H H	18.4454 16.8936 14.5827 13.3392 9.5842 12.8001 16.5982	9.3013 20.0511 18.2142 14.1462 14.4698 13.8880 20.2426	21.2420 11.7823 5.7668 17.7095 16.8748 10.0857 12.0679
	Ru Ru H C C C C	17.4458 8.7157 15.3505 10.3683 10.6107 10.3299 15.5338	17.1171 13.0967 18.5533 23.9640 23.1617 11.6932 21.9829	13.9100 11.5611 14.3387 15.8219 16.2374 17.0412 9.2654	C C H H H H H	17.6285 18.1255 14.1851 15.6088 14.6641 9.7299 12.5302	10.1934 20.5117 9.2254 21.5631 22.3754 14.9528 11.1310	20.3301 11.3483 9.0482 10.1587 12.9547 17.8008 13.6125
	Ru Ru H C C O C	17.4847 7.4486 16.2553 18.9534 19.4434 6.3112 16.2835	17.6369 10.6571 10.3006 21.9278 21.0420 15.7522 23.1095	18.1633 11.5893 9.4925 14.0909 14.3674 12.4333 19.6610	C C H H H H H	10.2110 19.2885 13.1056 12.1010 14.7191 12.9558 15.7952	22.5043 20.0153 10.0341 11.7895 22.2933 13.6021 15.5791	18.3987 11.9651 7.8677 14.3859 15.4924 17.0266 8.5078
	Ru Ru H C C O C	18.2016 4.9117 14.4835 17.7020 18.3120 7.6180 15.7554	11.3538 10.5833 14.7066 21.1470 20.0480 13.9394 21.9832	16.6621 11.6025 8.2578 14.3880 14.3293 12.0071 18.8067	C C H H H H H	11.0440 19.1590 12.4528 16.3469 12.5131 15.0699 16.6109	21.3890 19.0743 4.2827 16.1195 12.6878 22.3159 13.9488	17.8272 12.9749 21.3233 8.8090 11.3998 10.9777 10.0105
	Ru Ru H C C O C	18.0888 6.0947 12.9408 13.6139 13.7116 12.0205 12.3190	12.6399 12.8719 12.7581 13.6606 12.8635 16.4470 25.1276	14.4707 11.5800 8.2754 5.6508 6.0456 19.8812 11.8684	O C H H H H H	10.7704 17.8545 13.0323 16.4596 10.9427 12.9240 16.6447	20.9956 15.6326 5.6206 14.3952 15.2889 12.1728 15.3665	16.6320 12.2339 22.3597 10.0662 19.1647 11.9789 19.0536
	Ru Ru H C C O C	19.3527 6.2155 16.2710 13.6377 13.7613 13.1516 12.4659	13.7937 8.2845 16.4517 14.2924 13.4816 14.4829 23.6906	16.5134 11.7423 6.2393 7.0185 7.4189 19.7417 12.2978	O C H H H H H	11.9561 17.8086 14.0315 16.1137 13.7161 16.8600 16.8906	20.8797 14.5183 5.0873 16.1172 13.3016 17.3301 18.7150	18.5620 11.4119 21.0007 18.7988 18.0777 9.1091 17.8515
	Ru Ru H C C O C	18.1391 7.2078 14.9973 8.3879 8.5336 18.4208 12.9432	13.0282 15.1783 18.3011 11.0791 10.3410 19.2311 18.3916	18.7214 11.5335 11.8897 10.6739 11.1380 9.6347 5.6351	O C H H H H H	18.2155 17.2518 7.8850 16.3153 15.7323 16.9457 5.2481	11.2438 13.2030 13.7552 19.5090 20.7998 15.3190 12.9000	19.9014 13.3266 11.8098 17.8228 10.5015 10.0362 14.1209
	Ru Ru H C C O C	19.0660 7.3602 14.1977 9.2973 9.4850 19.3474 13.0106	14.9652 10.5326 18.8090 12.0701 11.2996 17.9473 18.2853	14.2049 7.4925 10.0237 11.3526 11.8054 11.2568 7.1374	O C H H H H H	16.4217 17.3110 10.1213 4.9141 12.5870 15.1185 4.8932	9.8077 14.3566 10.4861 14.0028 11.2878 15.8005 14.0902	20.1038 14.1188 22.4209 13.9657 13.4909 18.8835 12.8368
	Ru Ru H C C O O	19.0458 6.1986 13.4984 9.9185 10.2623 9.0132 6.6425	15.4213 9.7286 19.4169 19.5309 18.8462 19.8624 15.8692	18.4317 9.5597 7.7188 21.7741 22.2223 10.0369 14.0928	O C H H H H H	11.5358 17.0559 6.1774 4.4744 16.3090 15.0151 4.4980	9.5508 14.3905 19.4200 15.0939 15.5565 19.2964 14.4902	16.3194 15.5579 20.9484 12.6275 8.9808 18.2224 14.5177
	Ru Ru H C C O O	11.8757 6.2080 18.9714 10.3392 10.7038 9.6216 7.5939	11.3002 9.9438 17.3452 19.2808 18.5412 18.7418 13.7996	9.5088 13.7077 10.5128 20.3493 20.8139 8.1654 14.0724	O C H H H H H	9.9821 16.6638 4.7206 4.2465 16.6292 5.4456 14.7950	11.2517 13.2834 18.5829 15.6454 13.6249 12.6492 14.7829	16.3796 16.3200 20.3625 14.2996 10.2989 11.8985 22.9760
	N Ru H C C O O	10.9344 7.4680 20.5068 10.8965 10.1282 9.3893 13.7797	13.1085 10.7317 16.1409 11.5251 10.9105 22.2163 16.6509	9.2245 15.7154 4.7450 20.1582 19.6672 16.6856 20.5012	O C H H H H H	16.2331 16.5742 5.4221 13.9695 16.5274 4.9899 13.0544	16.8708 14.6837 19.8843 15.4044 15.2921 13.9011 15.1186	9.7682 18.2556 19.3771 22.6623 19.0940 10.7149 22.7953
	N Ru C C O O	13.3885 8.6012 11.2970 10.6003 8.7270 14.7232	12.5878 12.9317 12.4047 12.0796 23.0601 14.5873	10.1693 7.3751 19.0005 18.8435 14.6915 20.4534	O C H H H H	17.7899 16.9659 12.2985 16.6702 4.4109 14.1776	15.2325 15.7486 15.9700 18.7094 14.0442 16.4769	10.1153 17.4603 22.3840 18.1113 12.3871 23.0226
	N Ru C O O O	13.0330 7.2993 20.6588 6.6408 16.7621 18.1576	9.6970 12.1745 9.4640 15.8249 21.1820 16.8236	10.0720 9.5191 20.7016 14.1584 13.8724 8.8155	H C H H H H	13.9926 17.5013 13.5745 5.3297 12.7285 21.2909	12.5237 13.2604 17.1615 12.8286 14.2834 16.0945	7.5974 11.9548 22.7060 14.2896 22.2272 9.0730
	N Ru C O O O	10.4293 7.4264 22.0676 7.6339 16.5593 19.3261	10.0667 12.2362 9.4313 13.7892 20.6673 16.3778	8.7756 13.6528 20.3833 13.9551 16.0988 10.7018	H C H H H H	9.6901 16.4047 21.2614 4.8300 11.0293 20.9244	8.6151 13.4087 16.7298 13.9774 14.5964 17.8154	5.7912 17.6886 8.9425 13.0185 21.7862 8.8348
	N Ru C O O O	11.3913 8.7144 18.4793 13.7976 15.7472 9.1546	11.2084 13.0192 9.5944 16.6486 15.7935 19.1055	11.5072 15.7410 19.8276 20.5623 7.3748 11.0519	H C H H H H	9.4624 15.8570 20.9996 4.5728 12.0257 20.3696	9.7272 12.2643 18.4876 14.4071 15.9342 16.6361	10.5766 18.4942 8.8505 14.7202 22.3960 7.6195
	N Ru C O O O	12.3698 8.5087 17.9188 14.5879 13.5335 9.0280	11.2342 14.4936 9.6318 14.5199 15.4173 17.5776	7.5184 9.4756 21.0949 20.5312 7.0105 9.3808	H C H H H H	7.8237 14.3551 20.4127 14.6836 21.5564 7.0980	8.0949 12.1311 17.4575 14.7348 18.4782 18.9457	9.6451 18.1343 7.5262 23.0577 10.1239 8.5126
	C Ru Ru C O Ru O Ru O	13.3886 9.8576 11.6916 18.7670 18.3084 14.0827 10.4766 15.1200 11.2235	11.9095 15.3837 11.5882 9.5577 16.8984 16.7832 11.6171 16.1570 22.0625	6.9306 11.4129 19.3721 22.2148 8.9257 15.9704 10.9814 16.2634 17.2174	H C Ru H H Ru H Ru H	13.0544 17.4103 14.1680 7.5281 12.9818 16.6743 21.0208 17.6602 7.3611	10.9393 12.0466 11.5713 19.8587 15.2337 16.9729 20.1674 16.0637 20.3157	3.6883 11.0767 19.5109 7.6008 22.8873 16.4115 10.3061 16.0955 9.6565
	C Ru Ru C O Ru O Ru O	11.5706 8.5674 11.9389 20.1337 19.4303 15.0192 10.2763 15.0343 10.1365	10.4467 14.6402 11.6223 9.4776 15.8728 17.4119 13.2834 16.0611 22.7709	6.7196 13.6678 14.9656 22.0092 10.6059 11.7298 9.4679 11.8388 15.3624	H C Ru H H Ru H Ru H	11.1616 15.9782 17.5420 7.4696 14.2324 21.3622 20.8158 20.8225 6.4885	9.7018 11.6545 15.1783 21.0927 16.4801 9.8310 19.3626 8.2676 18.8646	4.7333 10.6979 8.7784 8.9172 23.0785 18.5449 8.7370 18.2283 10.1886
	C Ru Ru C O Ru O Ru O	10.4981 7.6979 12.0330 23.1031 9.4043 14.7543 9.4529 15.0963 16.8983	9.7617 6.1262 10.1115 9.4528 19.1430 15.5839 18.9214 14.5987 21.5779	7.4345 11.7476 17.1548 21.3385 10.9157 13.7055 19.5041 13.9847 15.7043	H C N H H N H N H	14.4985 12.7898 16.9653 6.7128 21.2983 21.2278 7.6731 20.3890 8.9922	12.4011 3.8720 15.8198 19.5026 15.6427 11.8399 19.9238 8.9133 24.4331	5.1641 15.9429 10.6510 9.1457 8.8554 18.0704 7.0621 20.1432 16.8960
	C Ru Ru C O Ru O Ru O	9.6080 8.8302 10.1851 23.6648 9.5447 12.4419 8.6389 13.7564 18.0573	8.8480 8.4108 13.7368 9.4016 17.7023 18.7547 16.8452 18.4686 19.6365	6.8522 7.4682 19.3301 18.6570 9.1769 15.9316 19.0633 16.2774 15.6012	H C N H H N H N H	9.1266 12.0651 19.0806 9.0638 21.1478 22.9925 7.2720 20.7289 10.6513	12.3658 4.8872 16.5408 25.6749 17.4125 9.9775 20.9413 10.2051 24.8292	8.5326 15.0831 8.6046 15.8599 8.8819 19.7938 8.4979 17.5560 17.4198
	C Ru Ru C O Ru O Ru O	9.4701 7.6314 10.5116 24.4279 11.3009 13.2463 10.2445 13.6140 14.5977	9.4586 7.6152 13.8573 9.4453 22.3536 19.5129 11.8356 18.4150 13.3474	9.5208 9.6191 15.0208 20.9375 16.9586 11.7296 15.7695 11.9330 7.9989	H C N H H N H N H	8.1251 5.5083 18.1625 10.6555 20.3935 21.7281 6.7464 21.4150 9.6748	14.5980 17.6163 14.8302 25.9133 16.5019 7.8447 19.2464 7.4672 23.7277	8.0676 14.6954 6.8419 16.6376 7.5511 18.9533 8.4266 16.4232 18.4096
	Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru C C C C C C C C C C C C C C C C C C C C C Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru N N N N N N C C C C C C C C C C Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O O O O O O O O O O O O O O O O O H H Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru O Ru O Ru O O Ru O Ru O O Ru O Ru O O Ru O Ru O O Ru O Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O O Ru H Ru O H Ru H Ru O H Ru H Ru O H Ru H Ru O H Ru H Ru O H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru H Ru H H Ru Ru H H Ru Ru H H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru H Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru H Ru Ru H	16.5634 16.4719 16.8198 14.9165 14.9104 13.8862 15.1470 13.8211 14.0652 13.5386 12.4641 9.9218 10.9470 11.4073 11.7952 12.3856 11.2350 11.2479 12.4641 13.4075 8.5660 11.8084 13.6643 12.8622 9.6838 9.1344 9.9167 11.1872 11.6987 8.6332 13.0207 14.7344 14.0984 15.8508 15.4891 13.6863 14.5877 14.1780 13.2391 12.4033 12.1568 11.5950 7.6842 8.9592 9.9553 10.1401 11.1962 11.4013 11.2170 11.1479 11.0920 10.4476 9.3789 11.4298 10.2399 10.2933 11.5093 12.5783 13.0057 12.6604 12.5368 12.6615 12.8742 12.8685 14.1608 12.8706 13.9963 14.0482 17.6784 17.1945 17.6200 15.7213 19.6685 17.9633 17.8810 16.9102 19.1520 19.4056 18.3984 17.1168 20.1355 20.5285 21.8599 22.3515 21.4859 8.9781 10.4690 9.3153 9.2182 8.9942 7.7796 5.2437 6.3863 6.6324 7.4320 8.0045 6.6851 6.3525 7.4307 9.1509 7.7945 7.5365 8.6006 8.9363 10.0386 8.6405 8.0995 9.3805 8.1073 7.9013 8.9535 10.6179 10.0585 11.7267 11.6342 11.2349 11.5254 11.2318 10.8422 9.6690 11.9532 10.7632 10.5042 11.5465 13.1798 13.2165 12.6161 13.1024 12.7426 13.2506 13.3589 14.5259 13.1105 14.4761 14.7285 15.0521 14.7575 13.4304 13.5522 12.0071 13.5705 12.2697 12.0892 12.2063 10.8282 8.2480 9.4805 9.3243 10.7174 11.0563 9.6296 9.3964 10.5542 12.3899 10.8786 10.7096 11.9199 12.1986 13.4353 11.9941 10.8375 12.3518 10.9194 10.6522 11.8492 13.7037 24.7162 20.2528 21.5154 20.3259 21.0176 21.6082 22.2851 22.0847 22.8553 23.3347 23.0350 18.1464 18.6014 17.3787 16.5213 16.9348 21.4851 19.5320 19.3772 20.2897 21.3629 20.1201 15.1884 15.0288 14.3288 19.0505 20.9026 6.3936 7.2614 13.2530 14.1523 18.2078 19.2462 9.2422 9.4261 11.0456 10.1410 16.7855 17.6115 14.7695 12.4976 9.7319 9.5857 11.0581 9.9770 11.5649 11.3172 8.9830 12.4123 15.0168 15.2673 15.0725 13.6797 13.7790 12.3229 13.8550 12.4627 12.3833 12.3898 11.1206 8.4979 9.6989 9.6676 10.9212 11.2248 9.8421 9.6882 10.9276 12.5370 11.0403 10.9719 12.2889 12.3115 13.7784 12.2630 11.1819 12.4848 11.1759 11.0787 12.3162 13.8635 13.6193 15.0858 14.9348 14.8698 14.8777 14.7308 13.9813 12.5832 15.1505 13.8466 13.7384 14.9915 16.5205 16.5123 16.2810 16.4517 10.3298 11.4774 10.7046 12.4166 12.3434 17.8443 13.1812 14.0034 13.7557 9.9549 17.8886 12.3075 16.1288 12.3002 9.6719 14.9029 12.1300 18.7358 12.3716 11.3765 12.6341 11.4425 19.2178 12.3479 10.3386 9.9856 10.5373 16.5399 11.1019 10.2938 9.7412 8.0033 16.9943 8.4803 11.6949 11.4675 8.8408 19.4036 9.6945 15.3678 10.3135 9.5044 21.2065 9.6271 15.4521 10.1565 9.7314 20.0084 10.8309 15.9039 11.4573 11.3224 19.8064 10.8458 15.2159 13.2604 9.7280 21.1220 9.6834 11.9377 13.4063 8.9788 21.6504 9.7993 13.0849 19.5948 9.6535 16.3135 11.0810 12.7412 20.7056 12.2810 20.5138 12.3734 13.3115 22.5518 10.6077 18.3823 10.9027 19.1522 23.1720 9.8426 23.2117 11.0703 21.3477 18.6385 10.6151 22.3251 12.4454 14.1976 19.1320 11.5174 23.3323 12.0896 14.0006 25.9849 12.4426 24.5599 13.4751 22.0302 24.5178 10.7621 23.1690 12.3337 22.5853 24.9757 11.3332 24.0383 11.2134 22.3420 21.1903 12.9324 24.9943 12.3018 21.6054 21.5115 11.3426 25.1486 11.0348 21.3574 20.9940 10.6377 26.0769 11.1558 20.6653 20.1934 11.3329 20.1607 12.4613 20.0567 21.4641 13.8937 20.6872 13.6087 20.1374 20.0761 12.2504 22.7055 13.7427 23.7850 20.5318 14.7845 24.5255 15.0491 26.0148 20.2657 13.9159 15.0817 14.9443 26.1411 21.3375 13.1250 15.9338 15.1345 24.0257 20.3915 14.0125 14.8918 22.1678 16.4879 13.1417 14.9678 19.8945 15.4744 14.0650 13.9467 17.9178 12.6339 12.9896 18.3290 15.5443 14.9544 22.7246 13.9280 13.6598 22.5408 13.2090 13.8003 18.3630 13.9291 15.1599 16.7153 16.4296 16.2515 18.3765 15.8324 16.4136 15.9519 14.8328 16.4231 9.0883 17.4940 17.6183 15.7166 16.4013 17.3414 17.7912 16.4399 16.3578 16.2010 16.2702 15.0635 16.3756 8.2921 15.8891 16.2479 11.1491	15.2789 14.6220 13.4700 17.3475 16.7308 14.8052 15.5135 14.2944 12.9854 17.6458 15.0968 14.9296 17.1742 12.6938 19.4914 14.5488 13.8754 14.5531 15.6169 17.1365 8.5505 10.3312 11.8317 11.0231 13.2815 14.5252 15.6656 15.5107 14.2180 8.2326 13.9706 12.2176 14.9606 13.1501 14.5655 8.8223 7.8879 8.7389 9.6477 10.5293 10.1623 10.2017 7.6321 8.5392 10.7379 10.8306 12.9663 13.2721 13.2116 14.6225 14.6459 6.3037 5.5726 8.5686 7.7320 7.7887 8.6939 10.8155 10.9574 11.1920 12.4708 12.4846 6.3837 7.9743 8.6068 7.7368 10.1524 10.1177 17.1779 15.6333 15.5766 17.6101 16.9627 18.6049 18.6237 19.4588 18.7448 19.7028 20.5427 20.4224 17.8320 16.0565 15.9631 16.8533 17.7802 11.3140 12.2537 11.4784 9.8160 14.5172 12.0620 11.9675 14.2284 9.6570 16.5557 12.1922 11.2317 11.2193 11.9800 14.5260 13.6286 13.5552 14.2360 15.9907 16.8011 15.9609 7.5168 10.0111 9.1072 8.9308 9.7304 12.3810 12.1362 14.6374 14.7160 14.4453 16.2302 16.0225 7.7668 6.9359 10.1901 9.2773 9.1857 10.0067 12.6223 12.4417 12.3646 14.0198 13.9296 7.8990 9.5190 10.2466 9.2308 11.7628 16.9586 16.8772 15.3768 19.1531 19.2333 16.8790 17.7212 16.8649 15.2370 19.9986 17.5894 17.7789 19.8489 15.3230 22.0825 17.5133 16.8065 16.9089 17.6529 19.9548 19.1381 19.1638 19.9783 21.4258 22.3383 21.4737 13.0030 15.4231 14.5905 14.5944 15.2444 17.6161 9.4192 6.4507 6.6905 5.0679 4.4706 5.2883 9.8881 7.6238 7.2584 8.2253 9.5751 8.4012 10.6916 10.9307 9.8897 8.5875 12.3287 11.7507 13.0731 14.0546 13.6576 15.5025 10.1130 11.3013 9.2345 15.7984 16.3487 16.9007 14.8121 17.3847 15.2976 17.8366 16.8339 19.9590 18.5305 23.1550 23.7883 21.1226 20.5446 14.5551 14.5027 11.7578 13.1498 20.1893 18.1893 11.8042 13.6604 21.5742 18.3993 16.1249 16.0849 14.5971 18.3262 18.4126 15.9891 16.8855 16.0525 14.4151 19.1294 16.7353 16.7690 18.9588 14.3947 21.2336 16.7185 15.9490 16.0424 16.8455 19.1593 18.2869 18.3005 19.1580 20.6435 21.5292 20.6675 12.1488 14.6275 13.7582 13.6326 14.4759 16.8271 16.7924 19.1631 19.3170 19.1894 20.7527 20.6653 12.2551 11.4659 14.5492 13.7397 13.6935 14.6224 16.9910 16.7812 16.8997 18.4901 22.9642 16.3063 12.6063 16.0156 13.5770 19.7582 17.6592 10.5010 16.8767 10.8504 19.6183 17.0455 11.2877 16.0608 12.2542 13.7517 15.1222 16.8705 14.4498 19.5223 13.6754 19.6980 15.5957 19.1851 17.5031 10.9428 17.2174 9.6590 16.7454 12.2828 12.4067 16.9739 10.0014 16.7981 12.9262 19.4074 19.2216 10.2377 18.9683 22.2231 17.4508 14.7534 10.1642 14.3612 20.8143 12.1962 21.6136 12.4355 21.2282 20.7916 12.8682 17.9062 14.7938 16.6719 22.2612 10.3411 16.6721 16.6469 15.8924 22.7963 9.4782 15.9871 16.1001 16.0212 23.4580 17.2495 16.6164 9.3143 16.8639 19.3503 18.0642 20.4322 9.3764 19.2233 17.1554 13.3853 19.1032 9.0956 18.2744 14.5625 7.6950 18.4097 7.9637 18.3205 14.9157 8.6768 19.0672 13.8319 19.1305 10.1925 6.3955 21.5183 12.2921 20.7336 8.0178 11.2640 22.2204 10.3744 21.5350 4.3508 9.2785 20.8657 12.0418 20.6446 5.6657 13.3710 12.7333 6.0857 12.1097 8.1904 9.1194 16.0502 7.8030 14.6215 9.2469 8.8861 14.6817 12.1126 13.7070 3.3690 10.8790 13.7914 9.9250 13.6608 2.3778 12.9797 14.5030 7.0402 14.5206 3.9359 5.8887 18.3010 4.6734 16.8913 6.3894 14.3158 16.9305 4.1816 16.8933 7.8045 14.8003 20.7229 8.1506 19.0761 7.9903 16.6060 20.1771 8.5851 19.2238 8.7576 12.2667 19.4661 8.4383 19.1225 9.2638 12.7301 21.9183 20.6365 9.6190 11.7959 21.1638 20.7398 10.1246 10.9374 13.2163 12.2044 9.8626 12.0091 11.4464 9.0709 16.2424 14.5790 10.6862 14.9825 13.7347 12.9973 14.2201 13.7519 12.2199 14.9872 14.6673 10.8971 18.7816 16.8640 6.3939 17.8484 16.8874 6.6941 17.4445 16.9489 20.6284 17.7703 16.1683 14.7519 13.9147 15.6921 14.6337 15.1563 13.7790 13.3046 12.3380 19.2051 18.4902 16.6218 19.8454 18.4393 18.2503	18.5110 14.2254 16.5645 18.2562 13.9421 18.5505 16.2915 14.3088 16.5948 15.9960 16.3489 16.3301 16.1237 16.8091 15.6812 12.1783 14.3530 18.4884 20.4431 11.9745 8.9907 5.3432 5.5728 4.7577 8.7308 8.4695 8.7205 9.2436 9.5259 7.6281 10.0862 10.2912 10.0121 10.2325 10.0182 9.2695 9.7520 11.9670 11.4291 12.2323 13.6187 13.7270 13.7094 15.8118 7.3548 15.7875 7.2563 11.5345 15.8025 9.4094 13.6441 11.6305 13.6541 7.3712 9.4799 13.7282 15.7481 7.2612 11.5097 15.8683 9.3854 13.6667 11.3641 9.4169 11.6957 13.6588 9.1960 13.6892 14.8576 16.1322 13.5644 14.3327 15.3559 13.4051 16.3122 16.7517 16.8570 17.8617 18.3004 17.7271 16.3303 14.8347 15.2100 16.1848 16.7379 19.1479 17.1270 14.8809 16.9389 17.0389 16.8944 16.6666 16.8416 16.8363 16.9668 12.7413 14.7421 18.8282 20.9818 12.8746 14.8385 18.9919 21.2130 14.9895 17.1365 19.1867 16.8901 12.8359 14.7903 18.9225 21.0889 12.8913 21.3356 12.9783 17.2271 21.4518 15.1966 19.3259 17.0059 18.9147 12.8327 14.8699 19.1048 21.3058 13.0412 17.3209 21.5488 15.2067 19.4186 17.0084 15.0799 17.3278 19.2981 15.1866 15.9926 11.6192 13.8585 15.8949 11.5113 15.8582 13.6957 11.5785 13.6351 13.7036 13.5688 13.3660 13.6301 13.5425 13.5505 9.4095 11.4673 15.5966 17.8388 9.4271 11.5092 15.6646 17.9319 11.6045 13.7622 15.8221 13.7405 9.4206 11.5076 15.6788 17.8919 9.4742 19.5602 18.7085 16.7379 18.6484 17.5777 16.6301 15.1880 15.7938 14.6719 13.8049 14.0655 16.3471 16.3211 15.6882 15.3512 15.6968 17.8135 16.6702 16.2401 16.6129 17.4388 16.2416 14.6861 14.0973 14.6941 15.4815 16.6647 13.7237 13.4806 20.1542 20.1568 8.7434 10.4911 10.3740 8.6243 16.5532 14.5769 13.4900 15.5118 7.5385 7.5828 12.5214 10.7439 19.7926 19.8003 17.8882 19.1892 13.4553 8.3511 16.3389 11.9811 14.2093 16.3149 11.9557 16.3108 14.1048 12.0205 14.1221 14.1746 14.0805 14.1036 14.1311 14.1511 14.0263 9.8901 12.0781 16.1530 18.3490 9.9432 12.0032 16.1421 18.3664 12.1347 14.1851 16.2763 14.1188 9.8367 11.9726 16.2543 18.3917 9.8922 18.4272 9.9772 14.1776 18.3502 12.0415 16.3787 14.1444 16.0718 9.8665 11.9644 16.2447 18.4315 9.9907 14.2066 18.3765 12.2731 15.0070 15.3656 17.8484 16.2557 8.0166 13.1748 13.6372 15.0108 14.0787 13.1469 15.4627 11.2148 14.6132 11.9547 11.3954 7.9120 13.0241 16.8124 14.1163 20.1899 8.0154 13.7095 14.9987 14.0728 20.2250 12.9286 13.0738 20.1708 14.0953 17.8301 11.2253 12.5762 22.5875 14.2989 19.4853 20.2476 13.1643 23.3462 14.1221 10.4984 20.2853 12.5758 21.6369 14.2499 8.7177 17.6538 13.5942 19.6396 14.1539 19.2674 19.3791 9.0122 18.9025 9.9140 17.6942 17.7644 10.7456 17.4381 12.2117 11.5536 15.6734 14.7661 15.8188 16.2363 13.3924 12.9958 17.2181 18.1188 18.3519 7.8072 14.7786 9.6334 15.5776 9.8806 7.6451 16.7160 11.2544 14.3480 11.9701 15.4686 18.7811 15.2742 16.8818 16.1395 15.9121 17.1533 17.7981 15.5423 18.4388 17.0607 18.0089 11.9216 14.5506 11.9575 16.4201 18.2660 14.3123 13.5592 14.1092 15.2004 18.5718 15.9304 19.7846 16.1972 13.1690 17.2883 12.5097 20.7350 14.2384 13.2534 14.9553 8.8829 21.4889 9.7869 15.3733 12.4962 10.6437 21.2868 12.0909 16.9314 11.0185 14.7749 22.1813 16.3322 19.0993 12.0796 17.1980 17.8621 18.3740 21.0077 18.8556 9.5025 18.4082 9.7628 20.6164 18.0160 17.7896 19.8682 18.3563 17.3754 13.1723 10.1656 14.7813 9.7225 18.4532 16.9399 14.2009 16.0875 14.0151 20.8696 19.6563 18.2513 14.5429 18.3133 22.0653 21.9135 12.3547 11.8847 22.9582 20.3252 16.5113 16.1457 23.8170 18.7163 12.9553 14.0270 22.2461 14.5329 16.1213 19.9358 9.4426 9.6933 17.8669 11.0586 11.8213 16.9151 15.2800 16.2011 16.1732 17.8126 18.3646 16.7699 10.1481 9.6983 17.8776 14.1909 14.0099 17.3072 18.2657 18.2612 13.9719 12.2877 11.9171 15.9313 16.1234 14.1010 13.9023 11.8040 11.8210 14.0513 14.0378 16.2678 16.0472 11.7789 12.4954 11.7754 9.1394	Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru H H H H H H H H H H H H H H H H H H H H H Ru C O O O O O O O O H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H N N N C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C O O O O O O O O Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru Ru N N N N N N C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Ru H N H N H Ru H N H N H Ru H N H N H Ru H C H C H Ru H C H C H Ru H C H C H Ru H C H C H Ru H C H C H N H C H C H N H C H C H N H C H C H N H C H C H N H C H C H N H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C H C C H C H C C H C H C C H C C C H C C C H C C C H C C C H C C C H C C C H C C C H C C C H C C C H C C C C C C C C C C C C C C C C C C C C H	12.1931 12.2808 13.4721 13.2729 14.4449 13.2202 13.0796 13.9926 12.8666 12.9660 14.0916 15.0085 15.0752 16.0402 16.1876 16.0798 15.7931 15.8716 15.8002 14.8062 9.5303 11.8008 7.9426 14.9337 13.8729 16.7818 13.4726 15.0852 14.3823 12.5384 9.7237 9.2992 15.5771 18.0955 18.3157 19.5107 11.7448 15.3632 10.7366 9.2710 9.9544 11.4161 6.3768 6.1172 7.3012 12.7273 10.8621 15.8811 15.0235 13.5199 14.1544 16.9906 16.5152 18.0045 18.0908 17.0920 16.3821 14.7721 12.4722 12.1676 14.1870 15.9795 18.1890 20.2809 20.0342 15.9326 16.2925 18.5964 20.4041 21.8442 23.3937 22.4967 20.1124 17.9858 17.8333 16.3736 15.9454 12.2727 12.8218 13.8270 6.8366 6.0299 4.6025 5.1944 4.5690 16.1845 18.7062 16.1645 18.0634 18.7533 20.0981 20.7495 20.0228 17.4028 17.0311 15.6481 14.4352 16.6580 15.8359 14.4930 13.9951 14.8476 15.6905 15.6226 14.6502 14.2573 19.7160 20.5443 21.2068 20.7881 16.0855 17.6556 19.2071 19.6971 19.1589 18.1135 14.8510 15.7957 16.1567 12.4858 13.6006 19.5030 12.9951 12.3097 5.6650 6.5091 6.3194 7.3524 12.9812 11.1331 12.7863 11.4770 14.6574 13.2803 13.2436 14.9613 14.8279 14.4774 14.7263 14.4364 13.5334 11.9535 14.9845 13.6072 13.3862 14.6192 16.3264 16.2094 15.9119 16.2341 16.0328 16.0511 16.2585 17.4508 15.9697 17.5992 17.3140 20.7359 21.8188 18.9818 19.8124 22.3628 20.8180 20.6057 4.8922 6.2852 9.4236 19.6565 18.6948 19.4196 12.7697 13.4722 14.5608 17.9759 15.0359 13.7529 10.1710 11.7701 13.2324 8.8361 18.0098 9.3689 8.1523 7.4603 8.8660 17.6965 9.0305 9.7371 10.7413 13.9542 11.1600 11.3600 9.8043 15.1124 20.8112 18.3595 16.8382 17.8519 22.8544 25.2291 25.7408 23.8472 19.7188 19.8486 21.0854 22.1436 23.0715 23.9296 23.3756 22.0425 18.4791 16.2925 17.0734 18.5294 22.3130 16.3258 7.5655 22.5777 7.2037 20.7747 20.0943 16.4526 7.5330 19.9337 8.6212 22.7100 19.1273 16.4939 6.8319 19.6404 7.4359 18.8715 19.2863 17.9571 9.3487 18.6261 18.4042 21.5119 12.6007 16.4131 10.9659 17.5643 17.3639 21.1368 12.9822 17.9130 9.7342 17.8160 18.7245 21.7089 14.3139 17.7057 20.0263 19.1500 14.2465 22.1249 17.7106 20.1886 19.0160 20.1616 15.1337 22.2530 17.0422 20.5719 20.0836 20.5152 16.0159 21.9432 13.4325 20.0272 12.8478 20.4129 17.6516 21.0925 10.6880 19.5182 13.5899 20.9359 15.3345 20.4079 11.2846 20.5487 14.6423 19.5233 13.6528 20.7054 13.7906 18.1828 17.7540 18.4657 9.0645 20.3608 9.2744 22.2071 15.2162 17.2310 11.4148 23.8759 18.0922 23.0251 13.8841 17.1590 11.6401 22.7617 9.7815 22.7524 10.4827 18.3717 8.1065 25.1170 8.2300 21.8230 11.9557 19.5654 18.0364 25.1824 7.5019 22.1606 13.6282 21.8082 9.6990 24.0016 8.8206 19.6319 9.2391 22.6228 9.2579 19.1581 18.1766 19.9169 18.2608 23.3318 8.5410 21.4806 9.0149 24.1096 9.7523 24.0166 10.1386 21.3007 9.7721 24.3742 8.2620 23.5024 16.6216 20.0336 10.6365 24.9305 7.6287 24.7026 7.2628 18.9342 14.9701 20.9963 8.9943 25.2176 7.7468 21.7776 10.7352 21.1695 18.0275 24.6133 8.8325 19.4992 10.0852 20.8846 9.3746 21.8838 14.7224 19.3472 9.1239 20.4503 10.0700 21.0090 10.2715 20.4365 15.9536 20.3040 11.0784 22.8130 10.3927 21.6769 16.4489 21.2088 14.3328 23.1713 8.8576 17.9788 16.3139 19.9345 10.2131 22.4297 15.2535 18.4324 14.8760 19.9926 10.7776 21.3122 17.0670 11.3234 20.0335 9.0985 23.9935 16.1495 15.8223 19.8825 15.2074 23.2685 16.6388 17.3703 19.8077 21.0724 14.6655 16.1066 20.2694 15.2767 20.3704 9.9418 19.7343 15.8371 5.2212 12.9688 17.5664 23.6023 6.5878 11.2726 18.1615 5.2549 14.0648 12.5545 17.4350 6.4871 14.2068 16.1858 16.0555 12.0449 20.5399 13.5455 17.5516 12.4403 19.2503 13.2774 16.1550 20.7953 7.3086 11.8959 18.3512 15.4280 13.9958 20.0453 5.2509 6.6094 17.0238 13.4449 17.9533 13.3383 8.7326 17.9617 7.9344 19.2002 8.8189 10.4473 7.5546 9.8903 19.4259 8.5941 13.8919	16.3664 16.9210 18.0201 18.8098 20.0182 19.3458 10.6269 12.4334 11.8916 12.4235 13.6358 14.9745 16.0600 17.4256 18.0014 18.4423 19.1052 19.6274 11.0797 10.5020 16.6634 16.3848 7.5159 11.1793 15.9373 12.7930 8.9049 7.2093 8.7572 9.2175 12.4239 12.0921 7.1630 8.2649 9.6473 9.3686 16.3455 14.6111 22.9927 22.0811 23.2287 10.1104 16.6593 16.4931 16.0411 5.9474 4.5901 10.8732 12.0611 12.8817 11.2077 12.2498 12.3179 14.6347 16.6169 16.7465 14.8503 16.2735 16.8252 18.5760 19.6654 20.4194 21.2441 20.3522 18.6595 19.3290 21.0662 21.2841 19.7778 18.4748 16.8131 15.2097 15.3907 12.1790 11.1651 11.3269 12.4723 2.9073 4.2434 3.7608 12.3205 17.9828 17.0818 18.4484 8.7265 16.6512 13.6130 13.6338 12.3991 11.2738 11.3633 12.5965 13.6814 15.3307 15.8583 17.5015 16.6615 12.4049 11.2654 11.3437 12.6232 13.7146 17.4598 17.3181 18.3139 18.6518 16.5661 18.2952 18.3212 17.4565 16.8813 13.9071 15.6308 15.4960 14.5531 13.7311 17.9825 17.0004 16.9641 10.3001 10.1309 17.3991 5.2333 6.2557 19.0552 18.0322 17.8727 17.3633 7.3218 5.9497 9.7273 10.9539 15.4477 17.2182 17.6071 19.9353 20.1095 19.9960 21.5154 21.4820 13.0279 12.5549 15.3249 14.4939 14.5562 15.4266 17.7933 17.6257 17.7310 19.1831 19.2177 13.1205 14.5621 15.2777 14.6483 17.0134 16.8584 9.3253 8.9569 9.4212 9.4942 9.4070 7.2670 11.3636 15.0494 15.6255 24.9517 21.8665 22.9766 21.5247 14.0473 12.5754 13.8370 18.7550 13.3067 20.7973 19.3900 21.5651 20.9944 17.5181 15.1628 13.7447 11.4036 10.9836 10.0907 17.4953 18.9406 20.5991 19.2242 13.9709 12.0010 10.5362 11.3917 18.5068 9.4269 9.5685 9.7160 9.6342 9.4799 9.4626 9.4099 9.3821 6.9492 4.4711 3.3863 4.8498 6.2067 7.9433 10.3749 10.9225 7.4053 7.7385 11.9823 13.3480 11.9944 18.4742 18.9664 9.9379 24.5668 6.2498 21.1977 12.2744 20.2137 9.8732 24.8842 8.3974 22.7140 13.8097 18.6058 9.5199 23.6678 8.3885 21.5825 14.5270 24.9018 9.7107 22.3294 6.0867 12.7901 13.9094 25.1168 9.7640 23.4108 5.4135 11.3286 16.3397 24.2016 9.9563 22.5918 8.1652 12.2598 15.9824 20.9156 10.0944 15.3898 7.5684 17.8443 11.3604 22.0567 10.0499 13.9764 6.1681 12.1519 11.0992 20.9093 12.7782 15.5003 5.4364 20.5499 13.3132 13.2443 14.0959 19.5043 4.0141 18.6395 11.7746 11.7749 15.9226 13.7177 5.6898 20.5283 9.4186 13.0603 16.1607 21.5039 3.4599 19.6022 11.0734 17.9361 9.5091 18.3337 4.3202 16.6167 11.4301 12.5042 9.3224 21.8931 8.1216 14.3081 12.4957 19.9800 9.1734 20.1024 8.7995 12.7156 10.2692 18.5441 9.1941 16.2051 8.2311 10.4619 9.1528 20.7752 9.3621 15.9340 8.6524 10.2536 7.8841 20.1876 13.5515 13.0079 8.9333 9.1805 8.4213 16.4492 11.1688 11.5938 9.2031 16.6928 7.1506 14.2839 11.3248 10.7217 9.0793 18.4566 10.2037 12.7296 10.2561 10.2470 9.5053 20.0928 12.4786 10.6977 8.7709 17.4899 9.7879 18.7387 11.3097 10.2448 11.1554 17.1544 9.6395 12.9826 9.9545 9.3464 9.9379 18.8759 11.0635 11.0590 9.8316 16.6698 8.7558 17.5626 10.6363 10.1930 10.9398 18.2612 12.2240 14.7249 11.9129 11.4642 12.1156 19.9195 6.7915 10.2706 12.7846 18.0987 12.1945 18.5786 7.5968 9.5462 12.3349 22.8035 6.8742 13.1047 6.2689 10.2345 7.3690 23.9495 13.4127 11.1282 5.2061 19.4950 9.6385 23.5065 14.4347 10.0540 5.4732 9.8820 11.2217 14.6908 10.6463 9.0192 8.8288 24.0577 15.7534 17.6909 8.9086 7.5397 23.1862 15.8632 14.5099 8.9845 22.9031 12.1633 10.4158 14.1755 15.2543 12.4223 9.0592 13.9674 25.7772 11.8889 11.1234 14.5845 25.4371 11.6210 13.7196 15.4878 25.2214 11.1928 14.5243 15.5881 13.1436 10.8559 15.0198 16.7947 17.6060 10.7126 15.3431 16.6494 19.3839 10.3146 19.2052 19.2258 18.2685 12.2871 10.3660 10.0086 17.1740 13.8896 14.5441 21.3382 13.1497 22.4815 12.3385 23.0546 20.9099 24.1068 21.6564 19.4895 22.8764 19.9410 24.0353 18.7550 18.5971 12.0296	14.0905 18.2421 20.1986 13.7566 15.7590 17.9128 17.1248 12.3733 14.6516 18.8080 20.7717 12.0708 20.4783 11.7756 15.9314 20.1616 13.6050 17.7911 16.8517 18.9777 8.5129 9.4565 7.1852 10.0282 9.5757 9.7686 8.2039 9.0610 13.0364 14.0051 11.5671 13.9997 11.5464 21.1832 22.2787 20.9950 12.1942 21.8390 19.2255 18.7845 17.6169 9.3826 13.9248 12.6753 14.5562 14.8070 14.7454 9.6801 11.4205 18.6355 17.2131 13.7867 15.8363 10.3456 11.8332 17.8781 19.3153 15.6085 14.8662 13.0539 12.0977 11.3189 10.5437 11.6696 13.4735 16.2876 18.0295 19.0745 18.2899 17.4962 16.5014 14.7492 14.0794 10.1509 11.5878 18.2529 19.5673 15.9286 16.9782 15.6037 7.5550 15.5859 15.0211 14.0545 11.2740 8.3013 9.4383 8.8343 9.5749 10.0589 10.3840 10.2180 9.7516 11.8360 13.0605 14.4214 14.8174 9.2072 9.2084 8.8487 8.5177 8.5215 11.8936 9.3730 9.1660 7.8810 7.3712 9.3821 8.1383 7.1436 10.6754 5.9903 6.4007 5.0837 4.2271 4.6940 6.7966 7.0513 13.1070 9.9023 8.8447 9.5636 21.3308 20.4477 20.0517 19.3418 18.0778 20.0302 20.2234 20.0317 11.0532 9.6376 15.1167 14.7282 18.0113 9.5646 13.8163 18.0313 11.6807 16.0382 13.9290 16.0415 9.5066 11.6249 15.8822 18.0959 9.6374 13.8591 18.0844 11.7470 15.9344 13.9781 11.8446 13.9663 15.9694 11.8188 16.0326 17.7693 16.0548 16.6773 19.6066 19.0305 17.7867 17.4355 13.6446 13.6199 17.4715 14.9272 13.8897 13.1807 5.0678 5.7661 5.1302 11.9059 11.7150 8.5516 17.4300 9.8471 18.7341 17.1339 12.1658 14.5568 9.6558 11.2560 10.6560 17.6347 22.0224 21.9376 22.4372 9.8952 21.1088 20.0710 20.1332 8.4145 22.8605 23.2258 21.1996 18.9386 22.3985 21.6760 19.1910 17.5831 19.5165 19.4242 17.4915 15.7890 14.4891 12.9364 13.4099 15.4265 16.6368 15.4645 15.5344 15.6043 18.4372 8.2264 16.8896 16.0188 18.6492 15.5038 16.1885 9.5309 20.0265 17.0584 19.0466 15.3392 14.3870 9.8105 17.4542 17.5642 17.5859 13.9710 12.1152 16.2792 19.6025 16.4410 16.3843 5.5615 14.0766 17.0096 20.5250 15.4790 17.6063 6.4883 16.2596 17.8946 21.8733 14.6838 15.3000 5.7463 12.1320 15.2844 22.2970 4.5475 14.1205 12.7122 16.3718 14.3446 21.3503 5.1541 14.0771 12.4859 16.8830 13.4893 18.7381 4.8842 15.2111 10.5062 14.8723 5.4882 18.3247 12.2564 17.7682 17.8917 16.2096 6.1505 16.6340 11.4726 19.8262 10.2714 18.7928 5.5034 16.1005 9.0343 18.9759 19.4227 17.4761 11.1253 18.1769 16.9445 20.0353 17.7692 16.6521 12.4432 17.5303 10.1471 18.4137 12.0499 17.3095 8.9726 16.1498 18.9175 20.3715 15.1152 17.1302 17.9127 15.4329 16.2764 19.0206 10.3859 17.8153 10.3595 16.1123 12.3513 20.3625 12.0060 17.9254 19.0865 16.4596 13.2951 21.0277 11.5061 18.4242 17.8421 16.2572 7.9262 20.6290 17.6511 17.5188 12.3624 15.0509 9.3210 20.9776 22.1651 17.9989 15.0286 14.4964 8.7233 22.3090 22.0871 18.1674 10.1397 20.2527 18.1104 22.7899 22.8446 17.4561 11.7546 21.0215 21.1627 21.9253 10.8498 17.9941 11.0744 21.5111 21.4096 17.4831 20.8478 14.2833 17.9448 21.1235 21.9041 17.1065 19.4093 12.9146 22.4843 16.9192 9.4248 16.5497 20.1826 12.1014 22.3368 18.4989 18.6616 16.4566 8.4979 12.6906 22.9102 19.7817 17.0169 16.9529 7.4964 14.0911 10.3171 20.1015 17.5674 17.6017 8.8837 18.4663 20.7373 19.6186 8.8568 17.2084 7.9299 14.8004 19.4295 18.8022 16.9791 15.8132 16.9354 19.4017 15.1667 17.0355 19.3658 14.1362 8.8324 16.3427 17.3084 19.5080 16.3766 17.1464 16.7911 20.7232 14.9372 14.9896 15.9050 10.4232 19.8466 15.4487 13.8800 12.4629 21.1015 20.1795 14.0320 12.0054 20.2111 11.7675 22.5642 10.8010 18.9639 12.1001 21.0649 17.6324 17.7848 21.7914 8.6895 5.1671 17.8000 20.3705 9.4579 5.3109 15.4644 9.8213 9.5500 5.3203 15.4209 15.1140 7.5011 14.0536 15.4547 6.2363 14.0312 15.9696 15.4941 14.2256 16.6917 15.0654 16.7157 8.8315 16.5983 16.6682 8.1508 17.3797 21.2833 10.2665 10.0220 12.2840
	Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez Roberto González Gómez					441 442 443 444 445 446 447 449 451

Domain 78, figure 5.5 (left) -Ru 55 (CH 3 COO) 2 (PS3)(H) 2 Domain 80, figure 5.6 (a) -Ru 55 (CH 3 COO) 10 (PS1)(H) 27 Domain 81, figure 5.6 (b) -Roberto González Gómez 448 Domain 82, figure 5.6 (c) -Roberto González Gómez 450 Domain 83, figure 5.8 (b) -

; (b) monodentate: η; (c) bidentate: μ.

d'échange de ligands). Cependant, l'efficacité du processus d'échange est probablement affectée par l'encombrement stérique des ligands. Illustration 18. Estimation de la surface initiale estimée de Ru x (C 7 H 15 COOH) 0,20 NPs et la nouvelle couverture de surface obtenue après l'échange de ligands avec 0,10 equiv. d'acide benzoïque. Une autre étude d'échange de ligands a été menée à partir des mêmes RuNPs préstabilisées avec l'acide octanoïque mais en utilisant l'acide trifluoroacétique comme ligand entrant. Le choix de l'acide trifluoroacétique (TFA) a été basé sur l'acidité plus élevée et le plus faible encombrement stérique qu'il présente par rapport à ceux de l'acide benzoïque. Les résultats obtenus ont montré une meilleure efficacité du processus d'échange de ligand que celui observé avec l'acide benzoïque. Les résultats du titrage par RMN ont indiqué que la surface des particules Ru x (C 7 H 15 COOH) 0,20 + 0,20 NPs préformée a été modifiée par substitution d'un peu plus de la moitié des ligands octanoates initiaux par des trifluoroacétates en ajoutant seulement 0,10 equiv. de TFA. En outre, la surface des RuNPs modifiées présentait une quantité plus élevée de ligands carboxylates, mettant ainsi clairement en évidence l' effet de l'encombrement stérique faible du TFA (illustration 19).

This thesis work was developed thanks to the Mexican financial support of the National Council of Science and Technology (CONACyT). I thus thank greatly to this institution for having awarded me the doctoral grant under the program "Becas de Posgrado en el Extranjero" (CVU: 483283) and thus promoting my postgraduate studies.

I would like to thank the current and former members of the team "Engineering of Metal

LIST OF SCHEMES

The elucidation of the NPs surface state is widely known in this field, there are several techniques that help to characterize MNPs. Some of them were used in this work, such as WAXS and HRTEM. [START_REF] Pan | A New Synthetic Method toward Bimetallic Ruthenium Platinum Nanoparticles[END_REF] Normally, the mean size and morphology of the nanoparticles are obtained by microscopy techniques [START_REF] Chen | Alkyne-Protected Ruthenium Nanoparticles[END_REF] and NMR experiments, such as DOSY, can contribute to corroborate the size of the MNPs by obtaining its hydrodynamic radii. [START_REF] Coppel | Full Characterization of Colloidal Solutions of Long-Alkyl-Chain-Amine-Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State, Equilibria, and Affinity[END_REF] While different techniques (FTIR, UV-vis, RAMAN, NMR, thermogravimetric methodologies, etc.) [START_REF] Pradeep | Noble metal nanoparticles for water purification : A critical review[END_REF] can be used to identify the nature of organic molecules present at the NP surface (like stabilizers, solvents, hydrides or pollutants) the quantification of these surrounding species is not so common in the literature.

Therefore, in the following section, it will be shown a well-defined surface mapping of the Ru x (C 7 H 15 COOH) 0.20 NPs. Experimental and theoretical techniques will be combined in order to estimate the quantities of stabilizing ligands and hydrides interacting with the nanoparticle surface. As previously done, NMR and theoretical tools will be mainly applied for this purpose.

NPs by 2D-NMR

Diffusion-Ordered NMR spectroscopy (DOSY-NMR) allows to determine the dynamic behavior of chemical compounds dispersed into a deuterated solvent. It is also a powerful tool to study the mobility of ligands attached or interacting with the surface of nanoparticles and to distinguish from free ligands in solution if any. [START_REF] Coppel | Full Characterization of Colloidal Solutions of Long-Alkyl-Chain-Amine-Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State, Equilibria, and Affinity[END_REF] This technique has already been used to characterize the surface composition of ethanoic-and pentanoic-stabilized RuNPs.

Firstly, a diffusion-filtered 1 H-NMR experiment was performed in order to see if the broad signal observed in the liquid 1 H-NMR spectrum ([0.5 -2. Roberto González Gómez 346 different conditions range were previously reported. [START_REF] Cusinato | Theoretical Characterization of the Surface Composition of Ruthenium Nanoparticles in Equilibrium with Syngas[END_REF] For this case, the study was performed at three different temperatures: 200, 300 and 450 K.

Normal Modes of Vibration

The normal modes of vibration were calculated with the VASP transitional state theory tools by using the dynamical matrix methodology which allows to find vibrational modes of pre-optimized structures.

[361]

Calculation of Atomic d-Band Centers

The coordination and averaged d-band centers ([172], [START_REF] Nørskov | Towards the computational design of solid catalysts[END_REF]) were calculated with the homemade tools4vasp suite of utilities, [START_REF] Cusinato | Shape, electronic structure and steric effects of organometallic nanocatalysts: relevant tools to improve the synergy between theory and experiment[END_REF] which uses the density of states (DOS) projected on a local basis set by the Lobster package. [START_REF] Maintz | LOBSTER: A tool to extract chemical bonding from plane-wave based DFT[END_REF] The atomic d-band center of an atom 𝛼, 𝜀̅ 𝑑 (𝛼) was calculated as follows. Besides, E min is readily set to the bottom of the occupied d-band. Finally, the DOS integrated up to the Fermi level (E F ). [START_REF] Del Rosal | Ligand-Field Theory-Based Analysis of the Adsorption Properties of Ruthenium Nanoparticles[END_REF]

pDOS, pCOHP and Atomic Charges Calculations

The projected density of states (pDOS) and the projected crystal orbital hamilton population (pCOHP) profiles as well as bond energy analysis were achieved with the Lobster software, using the pbeVASPfit basis set. ([362]- [START_REF] Maintz | Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids[END_REF]) Calculations in VASP were at least 12n + m +8k Hydrogen Adsorption Energies Roberto González Gómez 379

APPENDIX A

A.1 Adsorption of Hydrogen (H) onto Ru 55 NP