Y Liang

Y Lv

V Badets

A Bonnefont

L Ruhlmann

G Liu

X Yang

J Chen

W Dan

Z Chen

D S Wright

C Zhang

G Cai

X Wei

C Jiang

L Zhang

Y Ruhlmann

Lv

Y Shen

P Ma

S Zhao

C Wang

W Du

H Wang

LISTE DES COMMUNICATIONS : Oral

Fluorinated Oleophilic Electrochromic Copolymer Based on 3-(N-Trifluoroacetamido) thiophene

I would like to thank all the members of the research group for day to day support and their friendly behaviour. I would also like to sincerely thank my parents and my wife Fang CHEN for their unconditional love and support throughout this endeavour.

Yaokang LV Résumé

Introduction

Les clusters du type polyoxotitanate (POT) sont des complexes polynucléaires de titane, qui appartiennent à la famille des polyoxométallates (POMs) [1][2][3][4]. Les POT peuvent non seulement être considérés comme des systèmes modèles pour étudier le dioxyde de titane TiO2, mais sont également utiles en tant que précurseurs solubles de taille nanométrique pour la construction de nouveaux matériaux [5][6][7][8][9][10].

Les polymères conjugués ont attiré une grande attention pour une variété d'applications dans les dispositifs électroniques organiques, y compris les cellules photovoltaïques, les diodes électroluminescentes organiques, les transistors à effet de champ organique, les capteurs chimiques, les dispositifs électrochromes, les batteries et les supercondensateurs. La mauvaise stabilité des polymères conjugués reste cependant un obstacle majeur à leurs applications.

La préparation de composites inorganiques-organiques est un moyen efficace d'obtenir de nouveaux matériaux aux propriétés uniques. Cependant, les performances globales notamment électrochimiques des matériaux composites sont toujours limitées du fait de leur hétérogénéité à l'interface et de leur dispersion inégale.

Résultats et discussions

Synthèse et caractérisation d'une série de POT

Comme le montre la Figure 1, une série de POT avec des nucléarités différentes a été synthétisée et structurellement caractérisée. Leur diversité structurelle et leurs sites de coordination ajustables les rendent prometteurs en tant que précurseurs nanométriques ou blocs de construction pour de nouveaux matériaux.

Préparation et propriétés des nouveaux matériaux composites dérivés des POTs

En utilisant les POTs comme précurseurs nanométriques, comme nous nous y attendions, une série de nouveaux matériaux composites a pu être obtenue. Comme le montre la Figure 2, la composition de ces composites peut être radicalement modifiée par les conditions précises de calcination, telles que la température de calcination et la composition de l'atmosphère. calciné à différentes températures [300 °C (K300), 400 °C (K400), 500 °C (K500), 600 °C (K600), 700 °C (K700), 800 °C (K800), 900 °C (K900), et 1000 °C (K1000)] dans l'air (22% de dioxygène et 78% de diazote); (b) Diffractogrames DRX des matériaux composites calcinés à différentes températures [300 °C (N300), 400 °C (N400), 500 °C (N500), 600 °C (N600), 700 °C (N700), 800 °C (N800), 900 °C (N900), et 1000 °C (N1000)] en présence uniquement de diazote.

La Figure 3 présente la première courbe de charge et de décharge des matériaux composites obtenus dans la plage de tension de 0 à 3 V et une densité de courant de 50 mA/g. Les premières capacités spécifiques de décharge des matériaux K500, K600, K800 et K900 sont respectivement égales à 430,7 mAh/g, 181,6 mAh/g, 209,6 mAh/g et 35,9 mAh/g. Les premières capacités spécifiques de décharge des matériaux N500, N600, N800 et N900 sont respectivement égales à 942,6 mAh/g, 696,4 mAh/g, 515 mAh/g et 374,5 mAh/g. Figure 3. (a) Premières courbes de charge et de décharge des matériaux K500, K600, K800, K900 mesurées avec une densité de courant de 50 mA/g. (b) Premières courbes de charge et de décharge des matériaux N500, N600, N800, et N900 mesurées avec une densité de courant de 50 mA/g.

Préparation et propriétés des matériaux polymères hybrides préparés avec des monomères POT et des monomères dérivés du thiophène.

La diversité structurelle et les sites de coordination ajustables font que les monomères POT tels que Ti3O(TC)2(iPrO)8, Ti4O(TC)2(iPrO)10, et Ti6O6(TA)6(iPrO)6 peuvent être des blocs de construction de taille nanométrique pour la synthèse de nouveaux matériaux polymères hybrides conjugués. Ainsi, nous avons sélectionné et/ou synthétisé plusieurs monomères dérivés du thiophène pour préparer de nouveaux matériaux polymères hybrides tels que le 3,4éthylènedioxythiophène (EDOT), le 3-(N-trifluoroacétamido) thiophène (F-TH), le tris [4-(3,4-l'éthylènedioxythiophène)phényl]amine (TEPA) ainsi que la porphyrine 5,15-ditolyl de zinc (ZnT2P). De nouveaux films hybrides ont ensuite été préparés et déposés sur verre conducteur ITO par polymérisation électrochimique des monomères EDOT, TEPA ou ZnT2P en présence de divers cluster POTs : (Ti6O6(TA)6(iPrO)6) (POT-1) ou (Ti4O(TC)2(iPrO)10 (POT-2) (cf. Comme décrit sur le Schéma 1, de nouveaux films de copolymère hybride Poly-(H2T2P-POT-1) ont également été préparés par polymérisation électrochimique de la porphyrine monomère 5,15-(p-tolyl) porphyrine de zinc (ZnT2P) en présence du cluster Ti6O6(TA)6(iPrO6 (POT-1) sur électrode transparente du type ITO.

La formation des films jaunes bruns correspondant au copolymère Poly-(H2T2P-POT-1) a été obtenue par électropolymérisation. Celle-ci a été réalisée sous atmosphère d'argon en milieux NBu4PF6 0,1 mol L -1 + CH3CN / 1,2-C2H4Cl2 (3/7) contenant 2,5 × 10 -4 mol L -1 de ZnT2P ainsi que 2,5 × 10 -4 mol L -1 de POT-1. Des électrodes transparentes du type ITO, d'une surface de 1 cm 2 , ont été utilisées comme électrode de travail. Après électropolymérisation, les électrodes de travail modifiées ont été systématiquement lavées avec CH3CN afin d'éliminer les traces du sel de conductibilité NBu4PF6 et les monomères restant éventuellement sur les films électrodéposés.

Comme le montre la Figure 5, l'emploi du cluster POT-1 semble réagir avec le radical cation (ZnT2P +• ) électrogénérés lors des balayages voltamétriques itératifs [11][12][13]. Voltammogrammes cycliques enregistrés au cours de 25 premiers balayages itératifs effectués entre -1,50 V et +1,00 V / ECS en milieu NBu4PF6 0,1 mol.L -1 + 1,2-C2H4Cl2/CH3CN (7/3) avec ZnT2P (0,25 mmol.L -1 ) en présence de cluster POT-1 (0,25 mmol L -1 ). Electrode de travail : ITO. S = 1 cm 2 , v = 0,1 V s -1 . Courbe bleue : premier scan (n = 1). Courbe rouge : scan final (n = 25).

Comme le montre la Figure 6, les spectres UV-visible-NIR sur des électrodes ITO revêtues du copolymère ont été mesurés à différentes épaisseurs. On peut remarquer qu'au cours du processus d'électropolymérisation, la métalloporphyrine de zinc s'est démétallée et présente 4 bandes Q entre 500 nm et 680 nm au lieu de 2 initialement ce qui est typique de la présence de base libre H2T2P au sein du polymère que l'on pourrait nommer Poly-(H2T2P-POT-1).

L'intensité d'absorption du film, qui correspond à l'absorption des unités porphyrines, augmente linéairement avec le nombre de balayage itératif utilisé lors de l'électropolymérisation. Cela peut être expliqué par le mécanisme d'électropolymérisation libérant des ions H + . déposés sur électrodes ITO mesurée dans une solution aqueuse contenant un médiateur redox reversible 5 mM I2 / 0,5 M I -. Le potentiel d'équilibre du couple redox I3 -/ I -en solution est pris comme potentiel de référence à 0 V dans les voltamogrammes cycliques. La courbe obtenue en l'absence d'illumination a été analysée dans un premier temps (courbe noire). Pour l'électrode ITO nue (sans présence du copolymère), presque aucun courant faradique n'est observé entre -0,3 et 0,3 V, révélant que les cinétiques d'oxydation de I -et de réduction de I3 -sur électrode ITO sont lentes, ce qui est connu dans la litérature [14]. Cependant, les courants d'oxydation I -et de réduction I3 -

2) Conclusion générale

En résumé, cette thèse a permis la conception et la synthèse de plusieurs nouveaux matériaux qui ont été préparés à partir de cluster POT. Les Le film Poly-(H2T2P-POT-1) présente un bon comportement pour la génération de photocourant où le contrôle de l'épaisseur des films est d'une grande importance pour optimiser la génération de photocourant sous éclairage visible. L'efficacité de conversion globale η de la cellule scellée reste à étudier.

Nos travaux dans cette thèse ouvriront la voie à la fabrication de matériaux électrochromiques prometteurs avec d'excellentes performances intégrées et élargiront les applications des clusters polyoxotitanes.

2) Références The object of chapter III is to form a series of C@TiO2 composite materials. The C@TiO2 material N800 calcined in nitrogen flow at 800 o C exhibits excellent electrochemical performance, which is mainly attributed to the following aspects:

First, the nanoporous structure of N800 is beneficial to the transport of the electrolyte.

Second, the porous structure of N800 has a large specific surface area, which can increase the contact area between the electrolyte and the electrode. Third, the nanostructure can effectively shorten the transmission distance of lithium ions. Our work in this thesis will pave the way to fabricate promising electrochromic materials with excellent integrated performance and expand the applications of POMs.

Chapter 1

Introduction and literature review 1.1 World Energy Needs

In order to improve our daily life, worldwide scientists and engineers try our best to harness natural energy resources. After the first industrial revolution in the 18th century, massive coal resourses were exploited to produce energy, and the second industrial revolution since the 19th century introduced petroleum as fuel, fossil fuels have supplied major part of world's total world energy consumption at present.

However, fossil fuel reserves are facing a rapid depletion due to rapid rise in energy consumption in last few decades; limitation of available fossil fuels is an important factor for global oil crises [1] and wars in Middle East [2]. Besides, extreme use of nonrenewable fossil fuels caused undesired effects on natural environment, uncontrolled emission of carbon dioxide (CO2) and toxic gasses, responsible for global warming [3]. In 2015, the Paris Agreement concluded many years of negotiation and reset the aim of international climate policy to holding global warming to levels well below 2 °C and pursuing efforts to limit it to 1.5 °C [4],

Fulfiling domestic energy requirements to sustain industrialisation without increasing fossil fuels demand is the critical challenge nowadays. Thus, there is an increasing demand for effient and environmental-friendly technologies and devices for energy conversion, storage as well as application. Functional materials play a vital role and have important scientific significance for researches and developments.

Photo-electrochemical Cell

As the world's population grows and new economies emerge, novel solutions are necessary to provide energy to communities across the globe, this is one of society's basic needs. Solar energy is an inexhaustible, non-polluting and probably the most uniformly distributed energy source worldwide. In fact, "The amount of solar radiation striking the earth over a three-day period is equivalent to the energy stored in all fossil energy sources." Solar energy conversion and utilization is therefore one of the most important energy research topics recently [5].

Photo-electro-chemical (PEC) devices are used for the absorption of solar energy and its conversion to a usable form of chemical energy. As shown in One of the most important portions in a good PEC device is the photoactive semiconductor electrode material, which absorbs radiations with photon energy (hυ) greater than their band gap energy (Eg). In 1972, Fujishima and Honda firstly reported using single crystal TiO2 as a photo-anode materials of PEC devices for water splitting [7], since then, there has been a considerable progress in the research of PEC electrode materials. In 1978, Nozik provided an analytical account of the photo-electro-chemical devices [8]. In 1984, Heller gave an excellent analysis of efficiencies of various photo-electro-chemical systems [9]. In 1990, Getoff [10] and Pleskov [11a] gave a detailed analysis of PEC afterward. Around 2015, Gao's group [11b] demonstrates how PEC efficiency can be enhanced by optimizing the interface energetics and minimizing the reflectance of the surface. The stability of the photoelectrode was greatly enhanced by a thin TiO2 protection layer. The use of scarce materials can be significantly reduced by using bottom-up grown nanowires.

These improvements resulted in the highest photocathodic power-saved efficiency of 15.8% for single junction water reduction at that time [12]. In 2017, a new finding of cocatalyst-free and self-sensitized photocatalytic systems for splitting water into hydrogen by comparatively cost-effective Cu2X2-based MOFs have been presented

for the first time. It was a semiconductive MOFs material [13], and in 2019, the photo/electrochemical applications of a variety of metal sulfides (MSx)/TiO2 heterojunctions were summarized, and the authors' perspective on future architectural design and electrode construction is given in [14].

Energy Storage devices

Electricity is a fundamental building block in our modern world; the surplus electricity has to always be generated to meet varying demand. The total installed power generation using renewable energy (including hydropower, wind, solar, biomass, geothermal energy and so on) systems reached 2588 GW by the end of 2019 [15], but many available renewable energy systems like solar and wind are less predictable and more time variant. The integration of renewable energy systems with conventional power system brings several new challenges due to their intermittent nature. Energy storage is considered handy system and has better potential to improve the reliability of the power system. The integration with energy storage devices can reduce the complexities that arise due to the intermittent nature of renewable energy systems and could be used to reduce the power fluctuations. Both China and the United States are investing a considerable amount in adding energy storage devices and system to their electricity network [16].

Metal-ion batteries

Electrochemical batteries, which are one kind of the most efficient energy storage devices, have the advantages of facile storage and transport and high conversion efficiency. Metal-ion batteries (the metal ion could be Al 3+ , Zn 2+ , Ca 2+ , Mg 2+ , K + , Na + , Li + , etc.) have attracted extensive interest due to their high energy density and become the most popular electrochemical energy storage devices in the past several decades.

Metal-ion batteries have been widely used among the power system applications, their applied power reach to megawatts [17].

Usually, the electrode materials for metal-ion batteries are transition metal-based (e.g.

Co, Ni, Mn, V, Ti, etc.) inorganic materials which have the advantages of good capacity and high energy density. However, inorganic electrode materials always have limitation about resource shortage and environmental pollution. Furthermore, during charge-discharge cycling of batteries, the extraction/intercalation of the ions from/into the inorganic electrode materials always leads to volume expansion, phase transition and even pulverization, resulting in capacity decay [18]. Organic polymers have also been studied as electrode materials for rechargeable metal-ion batteries about 40 years.

There are a variety of organic polymer materials have been reported for metal-ion batteries [19]. Unlike inorganic materials, the volume expansion and structural variation of polymeric electrode materials are not severe due to their flexibility.

Conjugated polymers, especially the covalent organic frameworks with nanopores are remarkable electrode materials for metal-ion batteries. Conjugated polymers are superior in abundant surface areas, tunable chemical structures and nanopores that are even more remarkable for batteries with intercalation of large-sized ions. More importantly, these materials have the structural diversity and their electrochemical performance could be modified through facile molecular design. Therefore, the researches on these materials have become one of the most interesting areas for metalion batteries [START_REF] Xie | Nanostructured conjugated polymers: toward high-performance organic electrodes for rechargeable batteries[END_REF].

Supercapacitors

As another important kind of energy storage devices, supercapacitors have been widely studied in recent years due to their rapid charge and discharge rate, ultra-high power density and long cycle life. Mechanism of energy storage in supercapacitors could be considered as two phenomena: the first mechanism utilizes electrostatic accumulation of charge in electrical double layer and involves electrode materials with a well-developed surface area; thus, charge storage takes place at the electrode/electrolyte interface, the second one is based on reversible redox reactions occurring on electrode materials. Nowadays, supercapacitors have emerged as appealing alternatives to rechargeable energy storage devices in storage systems and renewable energy generation [START_REF] Sharma | Review of supercapacitors: Materials and devices[END_REF]. The research of electrode materials with stable structure, high electrochemical activity, large specific surface area and simple preparation process is the key problems for high performance supercapacitors.

Recently, various carbon materials with different porous morphology and physical

properties have been studied as potential electrode materials in supercapacitors [START_REF] Borenstein | Carbon-based composite materials for supercapacitor electrodes: a review[END_REF].

Much attention has also been focused also on conducting polymers such as polypyrrole (PPy), polyaniline, polythiophene, and their derivatives [START_REF] Snook | Conducting-polymer-based supercapacitor devices and electrodes[END_REF]. What's more, transition metal-based compounds are re-attracting attentions since their charge storage mechanism of reversible cations intercalation/deintercalation processes, and can be used as anode for asymmetric lithium-ion supercapacitors with improved energy density [START_REF] Lukatskaya | Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides[END_REF].

Electrochromic devices and materials

Electrochromism is the phenomenon where the optical transmittance or absorbance of a material or device changes changes under an applied electric potential as effected either by an electron-transfer (redox) process or by a sufficient electrochemical potential. As illustrated in Figure 2, due to the optical switching behavior, electrochromic materials provide great opportunities for energy-saving and colortuning applications, including architectural"smart windows", rear-view mirrors for cars, and display devices [START_REF] Granqvist | Electrochromic devices[END_REF]. Nowadays, commercial applications of electrochromic materials in devices include antiglare car mirrors, electrochromic sunglasses as well as smart windows for use in cars, aircraft, and buildings; electrochromic strips as battery state-of-charge indicators.

Through adjust the interior sunlight, smart windows could lower the energy consumption and improve the indoor comfort. There are many proposed applications for electrochromic materials such as protective eyewear, reusable price labels, glarereduction systems for offices, controllable aircraft canopies, camouflage materials, spacecraft thermal control, chameleonic fabrics, controllable light-reflective or lighttransmissive display devices for optical information and storage and devices for frozen-food monitoring, optical iris for camera lens [START_REF] Mortimer | Electrochromic materials[END_REF].

There have been reported a vast number of inorganic or organic materials exhibiting electrochromic properties, but only those materials with favorable electrochromic performance parameters are potentially useful since most of commercial applications require electrochromic materials with a high contrast ratio, coloration efficiency, write-erase efficiency and long cycle life [START_REF] Rosseinsky | Electrochromic systems and the prospects for devices[END_REF]. Inorganic electrochromic materials have emerged at the forefront for real-world applications and potential commercialization recently. Many inorganic electrochromic materials exhibit wide range of working temperature, long-term durability and good chemical stability.

However, most of these materials suffer from the shortcoming of poor switching speed which is due to the low electrical conductivity of the inorganic material, the slow ionic transporting efficiency and the high-volume expansion during cycling [START_REF] Li | Nanohybridization of molybdenum oxide with tungsten molybdenum oxide nanowires for solution-processed fully reversible switching of energy storing smart windows[END_REF].

Organic electrochromic materials, which are characterized by their fast response and rich color palette, are widely investigated [START_REF] Wang | Mechanical breathing in organic electrochromics[END_REF]. These classes of materials include organic molecules, polymers, and covalent organic frameworks. In comparison with the inorganic electrochromic counterparts, most of organic electrochromic materials exhibit inferior thermal and chemical stabilities, which therefore limited their practical use. Nanostructured surface of materials provides numerous active sites and shortens the ion's diffusion paths [START_REF] Cai | Inkjet printed large area multifunctional smart windows[END_REF]. Thus, as a means to further improve the switching speed, nanostructured electrochromic materials have been investigated in recent years. A nanostructured electrochromic material is expected to attain a rapid switching speed.

Materials based on polyoxometalates (POMs)

Metal oxides, which are the most dominant materials in the Earth's crust, have been shaping civilizational and technological developments for thousands of years. With the aim of discovering novel useful properties including electrocatalysis photocatalysis and electron storage that aid in solving urgent global challenges relating to clean energy production the demand and interest in the further exploitation of Earth's abundant metal oxides and their confinement to the nanoscale is greater and greater [START_REF] Sass | The substance of civilization: Materials and human history from the stone age to the age of silicon[END_REF]. Polyoxometalates (POMs) are combinations between oxygen and early transition metals at their highest oxidation states through atomic-precision synthesis.

POMs are molecular oxides which may also contain a variety of heteroatoms and often exhibit similar skeletal topologies of discrete nanoscale molecular formed during self-assembly processes [START_REF] Long | Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices[END_REF]. One of the most significant properties of POMs is the ability to accept and release a specific number of electrons without decomposing or change in their structural arrangements, there are numerous applications of POMs in catalysis, medicine and materials science [START_REF] López | Structure, properties and reactivity of polyoxometalates: a theoretical perspective[END_REF]. Currently, there has been a growing interest in diversifying the physicochemical properties of POMs by creating hybrid organic/inorganic POM architectures. These hybrid materials have been widely studied in the area of surfactants, catalysis, surface functionalization, light harvesting materials, eticular materials, non-linear optics, as well as charge storing materials [START_REF] Anyushin | Hybrid polyoxometalates as post-functionalization platforms: from fundamentals to emerging applications[END_REF]. POMs are ideal candidates for the development of a new type of supramolecular chemistry based upon the building-block ideas, they are set to become a paradigm for those working in nanoscale science.

Materials based on polyoxotitanates (POTs)

TiO2 based materials have drawn tremendous attention as highly stable and environmentally benign materials with a range of applications spanning from the paint pigment to semiconductors for sensors, energy storage and photonic devices. In particular, there is a growing interest on the application of TiO2 for solar energy harvesting. As widely used semiconductors, solid-state TiO2 with various nano-structural forms have been thoroughly documented in the literature [START_REF] Pelaez | A review on the visible light active titanium dioxide photocatalysts for environmental applications[END_REF]. However, mainly owing to the inherent difficulties in exploring dynamic processes at the TiO2 surface where chemical reactions occur (e.g., pollutant degradation, water splitting), detailed understanding of the TiO2 surface chemistry at the atomic level is still lacking [START_REF] Pelaez | A review on the visible light active titanium dioxide photocatalysts for environmental applications[END_REF][START_REF] Linsebigler | Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results[END_REF][START_REF] Sandell | Probing and modifying the empty-state threshold of anatase TiO2: Experiments and ab initio theory[END_REF][START_REF] Li | Oxygen-induced restructuring of the TiO2 (110) surface: a comprehensive study[END_REF][START_REF] Bai | Titanium dioxide nanomaterials for sensor applications[END_REF].

Furthermore, because of the insolubility of most TiO2 based materials, studies using solution-based analytical techniques are very hard.

Using recently developed synthetic approaches, the successful synthesis of atomically well-defined polyoxotitanates (POTs) allowed chemists and material scientist to gain new insights into molecular activation using TiO2. To date, as one of the most prosperous classes of POMs, POTs have been closely related to many photo-activities that broadly impact in the aera of energy and environmental sciences [START_REF] Rozes | Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials[END_REF][START_REF] Coppens | Crystallography and properties of polyoxotitanate nanoclusters[END_REF]. Besides, POTs bridge the gap between molecules and nanoparticles or bulk titania materials, and exhibits special intrinsic properties. Compared to TiO2 nanoparticles, POTs have at least two advantages. Firstly, accurate structural information on these crystalline materials can be acquired using an X-ray technique, which provides basic but precise structural data for theoretical calculations and mechanism explanation. Secondly, POTs stabilized by organic ligands are readily dissolved in organic solvents for recrystallization and postfunctionalization, and POTs serve as the building blocks for the bottom-up assembly of a variety of novel functional materials, too [START_REF] Li | Novel properties and potential applications of functional ligand-modified polyoxotitanate cages[END_REF]. Thus, these molecular materials with the same composition, size and shape can greatly overcome the imprecise and inhomogeneous characteristics of TiO2 nanoparticle materials.

Synthetic strategies of POTs

The synthetic approaches of POTs have been largely developed from traditional strict inert condition synthesis to solvothermal or ionothermal reactions, and even water phase synthesis in the past few years [START_REF] Narayanam | Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by πconjugated chromophores[END_REF][START_REF] Chambers | Maximizing the photocatalytic activity of metal-organic frameworks with aminated-functionalized linkers: substoichiometric effects in MIL-125-NH2[END_REF][START_REF] Lv | Encapsulation of a 'naked' Branion in a polyoxotitanate host[END_REF][START_REF] Lv | An integrated electrochromic supercapacitor based on nanostructured Er-containing titania using an Er (III)-doped polyoxotitanate cage[END_REF]. Most of reported POMs are polyanions, and could be synthesized in aqueous solution.

The metal atoms of these POMs are transition metals such as Mo, W, V, Nb, Ta in their high oxidation states. However, the poor degree of control of crystallization in a common water solvent has hampered the development of POTs, since Ti(IV) ions are easy to spontaneous hydrolysis in water which lead to an uncontrolled precipitation of TiO2. Recently, diverse synthetic methods have been developed to facilitate the acquisition of POTs attributed to the worldwide research efforts.

Schubert's group [START_REF] Czakler | Acetic acid mediated synthesis of phosphonate-substituted titanium oxo clusters[END_REF][START_REF] Artner | A heterobimetallic coppertitanium oxo cluster with a new structural motif[END_REF], Wright's group [START_REF] Lv | Encapsulation of a 'naked' Branion in a polyoxotitanate host[END_REF] and other forerunner groups developed a synthetic method where POTs were synthesized under strict inert conditions using easy hydrolysis of Ti(OR)4 as starting material, and a dry, O2-free atmosphere was used throughout all of the syntheses. Besides, solvothermal technique has also been proved to be a useful method in making crystalline POTs [START_REF] Lv | A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania[END_REF]. Compared to room temperature reactions, the high temperature and pressure can accelerate the solubility of the starting material, more components can be therefore employed into the reaction system, which enriches structural diversity and functional extension [START_REF] Gu | Chiral chemistry of metalcamphorate frameworks[END_REF][START_REF] Rocha | Luminescent multifunctional lanthanides-based metal-organic frameworks[END_REF]. In addition, the reaction cycle is largely reduced from several weeks in room temperature synthesis to several days in solvothermal synthesis. Reaction parameters in solvothermal synthesis could be controlled easily by setting the oven at different temperatures, required times as well as the warming up and cooling down rate.

Ti(OR)4 in combination with HO-R solvents are the most prevalent titanium precursors and have been extensively used to obtain POTs. Besides Ti(OR)4, there are other titanium salts like TiCl4 and TiOSO4, which can readily dissolve in water, forming highly acidic aqueous solution to prevent hydrolysis and can be used in the water phase reaction for the synthesis of POTs. For example, a series of POTs synthesized in aqueous solution have been reported by Wang's group [START_REF] Zhang | Water-soluble pentagonal-prismatic titanium-oxo clusters[END_REF][START_REF] Zhang | Small Titanium Oxo Clusters: Primary Structures of Titanium (IV) in Water[END_REF][START_REF] Hu | Effects of substitutional dopants on the photoresponse of a polyoxotitanate cluster[END_REF].

Compare to conventional solvents, ionic liquids usually act as both solvent and template for solvent-free synthesis which can reduce environmental contamination and potentially be more convenient than solvent-based synthesis. Recently, ionothermal synthesis has been extensively employed in the synthesis of inorganic zeolites and hybrid metal organic frameworks [START_REF] Xiong | Largest discrete supertetrahedral clusters synthesized in ionic liquids[END_REF][START_REF] Tang | Recent developments in deep eutectic solvents in chemical sciences[END_REF]. In 2017, a deep eutectic solvent synthesis approach has been successfully employed in the isolation of POTs [START_REF] Narayanam | Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by πconjugated chromophores[END_REF]. The anions in the deep eutectic solvents played an important role in the formation of the POT molecules. Although the ionothermal synthesis of POTs is still in its early stages, it is one of the most promising and environmental friendly synthetic methods in light of the variety of ionic liquids and deep eutectic solvents. Apart from one-pot reactions, two-step synthesis or stepwise method with a higher level of controllability was developed. Under these circumstances, the crystals of POTs are themselves used as the Ti source and precursors [START_REF] Chaumont | An unprecedented high nuclearity catecholato-based Ti (IV)-architecture bearing labile pyridine ligands[END_REF]66]. Furthermore, this stepwise approach can be used to obtain extended cluster based frameworks. As (ABZ = 4-aminobenzoate) as a precursor to a 3D framework combining the POT with photosensitizing porphyrinic linkers [START_REF] Yuan | A single crystalline porphyrinic titanium metal-organic framework[END_REF].

Structure of POTs

Development and improvement of synthetic methods contribute greatly to the structural diversity of POTs. In an important review reported by Sanchez's group, they systematically classified structures into three types according to their bridging ligands [START_REF] Rozes | Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials[END_REF].

Coppens' group summarized the high-nuclearity (>Ti10) POTs into seven detailed basic structure types [START_REF] Coppens | Crystallography and properties of polyoxotitanate nanoclusters[END_REF] while Zhang's group have introduced the up-to-date progress of POTs from low to high nuclearity [START_REF] Fang | Synthetic strategies, diverse structures and tuneable properties of polyoxo-titanium clusters[END_REF].

Modification with functional ligands is an important method to additional structural diversity of POTs. Bandgap measurements and bandgap calculations have clearly illustrated that this method will adjust the chemical reactivity of POTs [START_REF] Coppens | Crystallography and properties of polyoxotitanate nanoclusters[END_REF]. phosphonates, and carboxylates have been introduced as the functional organic species without changing the {Ti6} core. As confirmed by absorption spectra analysis, the increasing electron-withdrawing effect of the organic species allowed the gradual reduction of the bandgaps of POTs [START_REF] Liu | Bandgap engineering of titanium-oxo clusters: labile surface sites used for ligand substitution and metal incorporation[END_REF]. Materials generated by POTs from hydrolysis under various conditions is usually amorphous titania. Upon calcinating at 400 °C, amorphous titania will be converted to crystalline anatase and further to rutile around 500 °C [START_REF] Karatchevtseva | Crystallization of TiO2 powders and thin films prepared from modified titanium alkoxide precursors[END_REF]. Furthermore, the ligand-functionalised POTs under these circumstances can allow the conversion to titania to follow a different reaction route. For example, the tetranuclear cage [Ti4(μ4-O)(μfurfuryloxo)14] can convert to titania materials via cationic polymerization using trifluoromethanesulfonic anhydride as the initiator [START_REF] Mehner | Synthesis of Nanosized TiO2 by Cationic Polymerization of (µ4oxido)-hexakis (µ-furfuryloxo)-octakis (furfuryloxo)-tetra-titanium[END_REF]. Phase purity of converted titania materials can be fine-tuned through altering treatment conditions. Solely anatase phase of TiO2 can be obtain via pretreatment with excess distilled water at 100 °C before calcination at 400 °C produces, while mixture materials of anatase and rutile phases could be prepared through directly calcinating at 400 °C.

What's more, organic ligands not only act as sources of detrimental carbon impurities for titania crystallization, but also can be employed to produce novel hybrid titania materials. Self-assembled TiO2@C nanostructured composites have been produced

simply via calcinating the POTs in nitrogen atmosphere [START_REF] Lv | An integrated electrochromic supercapacitor based on nanostructured Er-containing titania using an Er (III)-doped polyoxotitanate cage[END_REF][START_REF] Liu | From a polyoxotitanium cage to TiO2/C composites, a novel strategy for nanoporous materials[END_REF]. As shown in Figure 8, through varying the type of POTs and the reaction conditions, the morphologies of the formed composites can be fine-tuned. POTs can also be used as nano-building blocks for hybrid materials construction.

Inorganic-organic hybrid materials combine the inorganic and organic components on the molecular scale to achieve a synergetic marriage of properties inherent to each constituent [START_REF] Férey | Hybrid porous solids: past, present, future[END_REF]. In synthesizing hybrid materials, the nano-building block based method is particularly attractive and POTs represent an important family of nanobuilding blocks [START_REF] Miele-Pajot | Synthesis and molecular structure of [Ti4(OPr i )8(μ, η2-OCH2CH=CHCH2O)2(μ3,η2-OCH2CH=CHCH2O)2]. Application to the elaboration of low density, microcellular, doped organic materials[END_REF][START_REF] Steunou | Synthesis of nanostructured polymer-titanium oxide composites through the assembly of titanium-oxo clusters and amphiphilic block copolymers micelles[END_REF]. Rozes and Sanchez have thoroughly reviewed the 'Lego-Like' construction of hybrid materials based on POTs as well as their syntheses, structures and nano-building blocks applications [START_REF] Rozes | Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials[END_REF]. As shown in Figure 9, the construction of POT-based hybrid materials is built upon the possibility of modifying these preformed POTs with polymerisable functional ligands, through which the polymerisable POTs can be inter-connected through ligand-induced aggregation, crosslinking, and metalorganic-framework formation. Substituting the more labile alkoxide groups into functional ligands, especially multidentate ligands can readily stabilize POTs against hydrolysis. Such substitution is regioselective and can be carried out in a controlled manner, paving the way for the broad use of POTs in hybrid materials construction [START_REF] Fornasieri | Reactivity of titanium oxo ethoxo cluster [Ti16O16(OEt)32]. Versatile precursor of nanobuilding blockbased hybrid materials[END_REF][START_REF] Frot | Ti8O8(OOCR)16, a new family of titanium-oxo clusters: potential NBUs for reticular chemistry[END_REF]. POT based material can be used as photocatalysts [START_REF] Li | Novel properties and potential applications of functional ligand-modified polyoxotitanate cages[END_REF] IR spectra analysis verified that the structures of POTs are retained on the electrode substrate, and a significant photocurrent was observed, confirming the photo-response of these POTs (Figure 12b). Both POTs show band gaps of ca. 2.5 eV that have been extended significantly into the visible region, although the utilized ligands themselves are transparent to visible light. Unfortunately, due to the non-conducting nature of the organic components, the magnitude of the photocurrent in both POTs is relatively small and the shape of the photocurrent plot is not an ideal square wave. A similar photocurrent response has been observed in 9-anthracenecarboxylic acid and catechol modified POTs, too [START_REF] Wu | Titanium-oxo cluster with 9-anthracenecarboxylate antennae: a fluorescent and photocurrent transfer material[END_REF]. Owing to the catechol HOMO energy level mixing with Chapter 2

Synthesis and Structures of POTs

Introduction

POTs containing well-defined ratios of Ti atoms to the dopant metals or organic ligands are very interesting since these POTs are potential single source precursors to useful materials such as metal-doped TiO2 with structurally well-defined models for metal-mediated photocatalysis. In this chapter, experimental details for the synthesis of several new POTs are summarized. The structure of these POTs are determined by single crystal X-ray diffraction, which are also presented.

Results and Discussion

Chemicals and Instrumentation

All chemicals used in this work were commercially available and used as received without further purification, unless specified. The growth process for the synthesis of POT-6, POT-7, POT-8, POT-9, POT-10, POT-11 is using solvothermal method.

Solvothermal synthesis is a commonly used method for preparation of different types of materials based on solution reaction-based approach. Compared to other synthesis method for POTs, there are obvious advantages such as the compositions of synthesized POTs can be well controlled, the simplicity and easy variation of process parameters. In general, solvothermal method involves crystallizing a substance at a high temperature and high vapor pressure using an organic solution. The processes of solvothermal reactions are carried out in autoclaves under controlled temperature and pressure, which

Synthesis and Characterisation of [Ti6O6(O i Pr)6(TA)6] (POT-1).

Titanium isopropoxide (1 ml, 4.8 mmol), Thiophene-3-acetic acid (TAH) (0.5g,

Synthesis and Characterisation of [Ti3O5(O i Pr)8(TC)2] (POT-2).

Titanium isopropoxide (1 ml, 4.8 mmol), thiophene-3-carboxylic acid (TCH) (0.13 g, 1.0 mmol) and isopropyl alcohol (4.5ml) were mixed in a glass bottle and heated at The sXRD data and refinement of POT-2 are summarized and shown in Table 2.

Selected bond lengths (Å) and angles ( o ) of POT-2 are shown in Table S2. The sXRD data and refinement of POT-3 are summarized and shown in Table 3.

Selected bond lengths (Å) and angles ( o ) of POT-3 are shown in Table S3. S4. S5.

Because the cost of synthesizing large amounts of POT-5 is relatively low, we further studied the preparation and application of a series of TiO2@C materials through calcination of POT-5. Till now, we have only obtained a few amount of POT-6, so that more studies of POT-6 haven't been done yet.

Synthesis and Characterisation of [Ti3O(O i Pr)9Cl] (POT-7).

Titanium isopropoxide (2 ml, 9.54 mmol), tungsten(VI) chloride anhydrous (0.397 g, 1mmol) and isopropanol anhydrous (7 ml) was placed in an autoclave under nitrogen S8. are listed in Table 9, selected bond lengths (Å) and angles ( o ) of POT-9 are shown in Table S9. S10. S11.

Synthesis of [Ti8O7(HOEt)(OEt)21Ce] (POT-12)

The In this chapter, we use POT-5 ([Ti 2O(OAc)2(HOAc)2Cl4] ) as precursor to obtain porous C@TiO2 materials through calcination in different atmospheres. These new materials are further used as anode material for lithium ion battery, their electrochemical performance is studied as well.

Results and Discussion

Chemicals and Instrumentation

All chemicals used were commercially available and used as received without further purification, unless specified. Powder XRD data was obtained by D/MAX-3C X-ray diffractometer from Rigaku Co., Ltd, using a Cu Kα radiation source (λ = 0.1541865 nm) with 2θ from 10˚ to 80˚. Fourier transform infrared (FT-IR) spectra were obtained by Thermo Fisher's Nicolet 6700 spectrometer, Scanning Electron Microscope (SEM) data were obtained by the FEI Nova Nano 450. The isothermal curves and pore size distribution were measured by the JW-BK122F type specific surface area and pore size analyzer. Particle size distributions were tested via dynamic light scattering nanometer particle size analyzer (Brookhaven Instruments Corporation).

Preparation of C@TiO2

The crystals of POT-5 were put into a tube furnace, then calcined in an air flow for 5 respectively were also conducted giving nanoporous C@TiO2 named N300, N400, N500, N600, N700, N800, N900, N1000.

Preparation and analysis of lithium-ion battery

The composite materials of C@TiO2 were used as the anode materials for lithium-ion battery. The mixture of C@TiO2, acetylene black and polyvinylidene fluoride (PVDF)

with the mass ratio of 8 : 1 : 1 was stirred until it becomes a slurry with an appropriate amount of 1-methyl-2-pyrrolidinone (NMP), then the resulting slurry was poured on the pure copper foil, using a spatula to scrape it on the copper foil evenly into a 90 μm thick film, and then baked in a vacuum drying oven at 60 o C for 12 hours. The dried copper foil was used as the anode, the lithium metal sheet was used as the counter electrode, and Celgard 2400 film was used as the separator. LiPF6 dissolved in ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate (EC/EMC/DMC) with a volume ratio of 1:1:1 were used as the electrolyte. Finally, the CR2023 button batteries were assembled in a glove box filled with argon.

Assembled CR2023 button batteries were placed at room temperature for 24 hours, and the galvanostatic charge-discharge test was performed on the LANHE CT2001A

battery test system at a voltage range from 0 to 3 V with different current densities.

CHI660E (Shanghai, Chenhua) electrochemical workstation were used for cyclic voltammetry (CV) test (from 0 to 3 V, scan rate 0.5 mV/s) and for Electrochemical Impedance Spectroscopy (EIS) test (from 100 kHz to 0.01 Hz) of the battery. In the XRD patterns of N900 and N1000, there are strong characteristic peaks of rutile, suggesting rutile TiO2 is the main component in these two materials. These results

Morphology characterization and analysis

show that compared to the calcination in air a higher calcination temperature is needed in inert nitrogen for transforming anatase component into rutile phase, which is probably because of the presence of considerable amount of carbon component that affects the phase transformation.

Figure 36. (a) IR curves about C@TiO2 materials of K300, K400, K500, K600, K700, K800, K900, K1000, (b) IR curves about C@TiO2 materials of N300, N400, N500, N600, N700, N800, N900, N1000.

Figure 36 displays the IR spectra of these prepared C@TiO2 materials. All the spectra exhibit board absorption bands in the wavelength range of 400-800 cm -1 corresponding to the Ti-O bond. As shown in Figure 36a, the IR spectrum of K300 has a broad absorption band around the wavelength of 3200 cm -1 , which may correspond to stretching vibration of hydroxyl group. Besides, there are absorption peaks around wavelengths of 1636.1 cm -1 , 1533.4 cm -1 , and 1411.8 cm -1 , which may correspond to symmetric (s) and asymmetric (as) stretching bands of carboxyl group. These results suggest that there is considerable amount of active components that have not been destroyed in K300. However, we can not find similar significant peaks in the IR spectra of K500, K600, K700, K800, K900, K1000, indicating most of active components were destroyed as the calcination temperature increases. As shown in Figure 36b, the IR spectrum of N300 is similar with that of K300, suggesting considerable amount of organic compounds. But there are weak bands around the wavelength of 3200 cm -1 and 1500 cm -1 in the IR spectra of N400, N500, N600, N700, N800, which suggest the existence of active group like hydroxyl group and carboxyl group respectively. Both hydroxyl group and carboxyl group exhibit electrochemical

The SEM images of K500, K600, K800, and K900 are shown in Figure 37. These materials are composed of small irregular particles. It can be found that the K600, K800, and K900 particles are much tightly packed than that of K500. Figure 38 shows the SEM images of N500, N600, N800, and N900. The materials' particles are stacked on top of each other, and there are a large number of fissures between the particles, which can be beneficial for the moving of ions. As shown in Figure 39, the average particle size of N500 is with a bit larger than that of K500, but the particle sizes of N600, N800, and N900 are significantly smaller than that of K600, K800, and K900, indicating that the presence of carbon can inhibit the growth of crystals, resulting in a smaller particle size. As the calcination temperature rises, the porosity decreases and the crystal size increases. Figure 41 shows the pore size distribution of the products K500, K600, K800, K900, N500, N600, N800 and N900. The pore size distribution of all these materials are mainly concentrated in the mesopore range. The specific surface area, pore volume and average pore diameter of these materials are listed in Table 12. With the increase of the calcination temperature, the specific surface area and pore volume of the C@TiO2 materials are decreasing because of the phase transformation from anatase to rutile, while the average pore diameter does not change much, which is due to the decomposition of the organic ligands. The specific surface areas of N500, N600, N800 and N900 are 98.914 m 2 g -1 , 46.518 m 2 g -1 , 66.356 m 2 g -1 , 54.036 m 2 g -1 , which are significantly higher than that of C@TiO2 composites (K500, K600, K800 and K900) calcined in air atmosphere at the same temperature. The carbon component inhibits the growth of crystals and can increase the specific surface area of the C@TiO2 composites.

Electrochemical properties

To study the redox potential of the materials and the mechanism of lithium ion insertion/extraction and its electrochemical reaction, cyclic voltammetry (CV) analysis was first used for scanning the lithium battery at a constant sweep rate within a specified voltage range.

CV curves of a series of C@TiO2 composites based lithium-ion batteries with a potential scan rate of 0. Figure 43 shows first cycle of galvanostatic charge-discharge curves about these C@TiO2 composites with current density of 50 mA/g and the voltage range of 0-3 V.

All of these materials have charging and discharge platforms between 1.68 V and 2.10

V, which are consistent with their CV results. As shown in Figure 43a, the first discharge specific capacities of materials K500, K600, K800 and K900 are 430.7 mAh/g, 181.6 mAh/g, 209.6 mAh/g and 35.9 mAh/g, respectively. As shown in Figure 44a and Figure 44b show the rate performance of a series of C@TiO2 composites as anode materials. As shown in Figure 44a, the materials calcined in air (K500, K600, K800, K900) show good rate performance. Their discharge specific capacity decreases regularly as the current density increases from 50 mA/g to 250 mA/g. But the reduction is relatively small, when the current density is restored to 50 mA/g, the specific discharge capacity of the material can also be restored to the initial value. The specific discharge capacity remains stable at the same current density, which is mainly due to the mesoporous structure of the C@TiO2 composites. As shown in Figure 44b, the materials calcined in nitrogen (N500, N600, N800, N900) also have excellent properties. N500, N600, N800, N900 have higher discharge capacity than K500, K600, K800, K900. Cycling stabilities of these materials are shown in Figure 44c andFigure 44d. At a current density of 50 mA/g, the initial specific capacities of K500, K600, K800, K900 are 365.9 mAh/g, 291.5 mAh/g, 250.3 mAh/g, 86.9 mAh/g, respectively. While after 100 cycles, their specific capacities drop to 20.8 mAh/g (K500), 113.1 mAh/g (K600), 95.4 mAh/g (K800), 39.9 mAh/g (K900), the capacity retention rates are 5.7%, 38.8%, 38.1%, and 45.9%.

The initial specific capacities of N500, N600, N800, N900 are 629.3 mAh/g, 345.1 mAh/g, 446.7 mAh/g, 90.2 mAh/g respectively. After 100 cycles, the capacity is 295.6 mAh/g (N500), 192 mAh/g (N600), 340.4 mAh/g (N800), and 76 mAh/g (N900), while the capacity retention rate is 47%, 55.6%, 76.2%, 84.3%. The C@TiO2 composite material N800 has the best performance.

Conclusions

In summary, the C@TiO2 composite materials calcined in nitrogen flow N800 exhibits excellent electrochemical performance, which is mainly attributed to the following aspects: First, the nanoporous structure of N800 is beneficial to the electrolyte. Second, the porous structure of N800 has a large specific surface area, which can increase the contact area between the electrolyte and the electrode. Third, the nanostructure can effectively shorten the transmission distance of lithium ions.

Fourth, the carbon component in N800 can increase the conductivity of this composites which ensures rapid charge-discharge, and good rate performance. POTs can also be employed as 'nano-blocks' for the formation of new organicinorganic hybrid materials. For example, the introduction of styrenic groups allows copolymerization of the POT building block Ti16O16(OEt)32-x(OPhCH=CH2)x with styrene to form hybrid three-dimensional network materials in which the titania nanofillers are covalently linked to a non-conjugated organic polymer.

In addition, particularly pertinent to the studies presented here, are conjugated thiophene-polyoxomolybdate polymers which have been used in photovoltaic cells [145,146]. However, the synthesis of these materials requires a three-component chemical coupling procedure.

In this chapter, we designed and synthesized a series of conjugated polymers, and further combined conjugated polymers and POTs to obtain novel organic-inorganic hybrid materials using different methods. The electrochemical properties and photo electrochemical properties of these novel materials are studied.

Results and Discussion

Chemical and Instrumentation

All reagent grade chemicals were purchased from The Aldrich or Aladdin Reagent Average molecular weight and polydispersity indices (PDIs) were measured through gel permeation chromatography (GPC) using a Waters Breeze 2 HPLC system.

Scanning electron microscopy (SEM) images were collected using a field emission scanning electron microscope (Zeiss Gemini 300). Measurements of surface area and pore size were carried out using an ASAP 2460 surface area and porosimetry auto analyzer (Micromeritics, USA). Ultraviolet-visible (UV-vis) and near infrared (NIR) spectra were obtained using a UV-1800 spectrophotometer (Shimadzu, Japan).

Synthesis of organic monomers

Synthesis of 3-(N-trifluoroacetamido)thiophene (F-TH)

3-Aminothiophene oxalate (1.89 g, 0.01 mol) was dissolved in dichloromethane (40 ml), then triethylamine (2.53 g, 0.025 mol) was added. After the mixture solution was stirred and cooled to 0 o C in an ice water bath, trifluoroacetic anhydride (2.52 g, 0.012 mol) was added dropwise slowly and reacted at room temperature for 2 hours. At the end of the reaction, saturated NaHCO3 solution was added until no bubbles formed.

The reaction mixture was extracted with ethyl acetate three times, and the organic phase was combined. The organic phase was washed three times with saturated NaCl solution, dried by anhydrous Na2SO4, filtered, and evaporated. Table 15 Hydrogen-bonding geometry (Å o ) of F-TH. Symmetry codes: (i) -x+1/2, y, z+1/2; (ii) -x-1/2, y, z-1/2; (iii) -x-1/2, y, z+1/2.

D-H•••A D-H H•••A D•••A D-H•••A N1_1-H1B••• O1_1 i 0.
The distributions of the highest occupied molecular orbitals (HOMO) and the lowest In detail, TEPA was obtained via a four-step synthetic route:

Step 1: synthesis of 2-iodo-3,4-(ethylenedioxy)thiophene (1).

A hexane solution of n-BuLi (16.1 mL, 2.4 M, 38.7 mmol) was added drop-wise to a solution of EDOT (5 g, 35.2 mmol) in tetrahydrofuran (THF, 50 mL) at -78 °C. The mixture was stirred for one hour at this temperature, then iodine (8.9 g, 35.2 mmol) in THF (50 mL) was slowly added to the solution, whereupon the red color slowly disappeared. After one hour of stirring at room temperature, water was added and the mixture was extracted with diethyl ether (3×100 mL). The combined organic layers were washed with aqueous Na2SO3, saturated NaHCO3 solution, water and brine (100 mL each). The organic phase was dried over MgSO4. After filtration and removing the solvent under vacuum, the white powder 1 was purified by recrystallization from ether (8.0 g, yield 84%).

Step 2: synthesis of 4,4',4''-Tribromotriphenylamine (2).

A solution of N-bromosuccinimide (NBS, 25 g,100 mmol) in N,Ndimethylformamide (DMF, 100 mL) was added drop-wise to a solution of TPA (10.0 g, 40.8 mmol) in DMF (100 mL) in a three-necked flask at 0 °C. The mixture was warmed to room temperature, stirred for an additional 12 hours, and then poured into excess water and extracted with CH2Cl2. The combined extracts were washed with brine and dried over MgSO4 and then the solvent was evaporated under vacuum, the crude product of 2 (50 g, yield 100%) was obtained and used in the next step without purification.

Step 3: synthesis of Tris[4-(

n-BuLi (2.5 M in hexane, 85 mL, 205.4 mmol) was added dropwise to a solution of 2 (30 g, 62.2 mmol) in anhydrous THF (300 mL) at -78 °C under N2 and the mixture was stirred for 2 hours. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (40.5 g, 217.7 mmol) was added in one portion to the mixture, which was then warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, the crude product was dissolved in CH2Cl2 (500 mL) and washed with water (3×200 mL). The organic phase was dried over MgSO4, and the product of 3 was precipitated by reduction of the volume of the solvent to ca. 50 mL as a white solid (36.0 g, yield 64%).

Step 4: synthesis of TEPA.

A mixture of 1 (1.5 g, 5.6 mmol), 3 (0.9 g, 1.4 mmol) and K2CO3 (1.9 g, 14 mmol) was suspended in 30 mL of dioxane in a Schlenk flask. The air was removed by 17 and selected bond lengths (Å) and angles ( o ) as well as hydrogen-bonding geometries are listed in Table 18 and Table 19. The dihedral angles between the two aromatic rings of TEPA molecule were calculated using the Diamond software. The calculated dihedral angles are summarized in Table 20. As shown in Figure 56, molecules of TEPA have a highly distorted arrangement. The three phenyl groups of the TPA core within individual molecules are not in the same plane, with the dihedral angles between the neighboring phenyl groups of TPA core being in the range of 59.9-74.5 o (Figure 56a). In addition, the phenyl and thiophene rings are also not co-planar, with the dihedral angles between these rings being in the range of 18.6-23.3 o (Figure 56b). These features are important because, in general, planarity and the resulting conjugation are strongly related to the band gap and conductivity of polymers, while the planarity of monomer units determines the planarity of the conjugated polymer to a large extent, small conformational differences may produce large band-gap effects in conjugated polymers [151][152][153][154].

D-H•

••A D-H H•••A D•••A D-H•••A C1B-H1BA•••O2Ei 0.
The structure of the TEPA monomer is therefore not only related to the conformation of PTEPA but also to its physical properties. Figure 57 shows two possible assemblies of TEPA, although it is possible to assemble a nanoring through three connected TEPA molecules (shown on the left of Figure 57b) which would form the previously proposed honeycomb sheet arrangement, the inherent distortion of the building blocks of TEPA are, we believe, more likely to result in the formation polymer chains (Figure 57b, right). In this case polymerization of TEPA would result in irregular spiral channels (Figure 57c) instead of the ordered columnar channels which would occur in a honeycomb structure. As shown in Figure 57d, cross-linking of this arrangement will give a three-dimensional porous dendritic structure. As the degree of polymerization increases, the effect of the bifurcation and distortion of PTEPA will be accumulated throughout the structure of the polymer, while the pores and channels in PTEPA will be also gradually twisted and blocked by the external branches. This less porous structure is consistent with porosity measurements of PTEPA (see section 4.2.3.2). It was reported that Polytriphenylamine (PTPA) displays negligible microporous structure with a very small surface area, which, it was proposed, may be due to the difficulty in building a porous honeycomb structure using a monomer with shorter connecting groups. Based on this hypothesis, we speculate that the structure of PTPA contains similar twisted pores and channels to that proposed for PTEPA.

Preparation and properties of conjugated polymers

Preparation and properties of P(F-TH) and P(F-TH:EDOT)

The conjugated polymer film of P(F-TH) was prepared via constant potential polymerization onto the ITO substrate at 1.9V vs Ag/AgCl. Electrochemical polymerization was performed in 0.1 M TBAPF6/ CH3CN containing 0.03 mol•L -1 F-TH and the amount of electricity accumulated on the films of ITO glass (0.9 cm × 2.6 cm) was 0.06 C using a three-electrode system with Ag/AgCl reference electrode and Pt sheet counter electrode. After that, P(F-TH) was dedoped at -0.6 V for 1 minute.

The film of P(F-TH:EDOT) was prepared via constant potential copolymerization of the F-TH and EDOT monomers onto the ITO substrate at 1.4V. This electrochemical copolymerization was performed in 0.1 M LiClO4 / CH3CN solution containing 5.0 mmol•L -1 F-TH, 5.0 mmol•L -1 EDOT, and the amount of electricity accumulated on the films of ITO glass (0.9 cm × 2.6 cm) was 0.05 C using a three-electrode system with Ag/AgCl reference electrode and Pt sheet counter electrode. After that the P(F-TH:EDOT) film was dedoped at -0.8 V.

The film of PEDOT for comparison was also prepared via constant potential copolymerization of the EDOT monomers onto the ITO substrate at 1.4V.

Electrochemical polymerization was performed in 0.1 M LiClO4/ CH3CN containing 5.0 mmol•L -1 EDOT, and the amount of electricity accumulated on the films of ITO glass (0.9 cm × 2.6 cm) was 0.05 C using a three-electrode system with Ag/AgCl reference electrode and Pt sheet counter electrode. After that, the PEDOT film was dedoped at -0.8 V. In order to evaluate their properties, the P(F-TH:EDOT) and PEDOT films were electrodeposited onto ITO coated glass having dimensions of 2.6 cm × 0.9 cm at a constant potential of 1.4 V versus Ag/AgCl and passing charge of 0.05 C to form films with an average thickness of ~86.9 nm for P(F-TH:EDOT) and ~85. In order to characterize the optical contrast (ΔT%) and switching properties of the PTEPA film, dynamic electrochromic experiments were studied at 440 nm and 660 nm. The square wave potential method was used between -0.4 V and 1.0 V at regular intervals of 5 s. As shown in Figure 67b, the ΔT% was found to be 23.97% at 440 nm and 14.29% at 660 nm, which were are slightly lower than that of electroploymerized PTEPA films (26.84% at 448 nm and 17.03% at 660 nm). The coloration efficiency values of PTEPA film are calculated to be 80.6 cm 2 /C at 440 nm and 122.8 cm 2 /C at 660 nm, respectively. In addition, the switching time of the PTEPA film was found to be 0.96 s for coloring and 1.89 s for bleaching at 440 nm (Figure 67c), and 0.67 s for coloring and 2.89 s for bleaching at 660 nm (Figure 67d).

These times are longer compared to electroploymerized PTEPA film. These phenomena can be attributed to the relatively low polymerization degree of the dropcasted film. The reasonable optical contrast and the fast switching properties make PTEPA a promising electrochromic material and will be beneficial to its application in electrochromic supercapacitors (ECSCs). As shown in Figure 68 (A,C,E,G,I,K), all the PEDOT films grown in DCM show twisted nanofibers structure, which is significant different with the PEDOT films grown in ACN (Figure 68B,D,F,H,J,L). As a solvent, DCM solvent exhibit greater volatility and smaller viscosity than that of ACN, which accelerates the diffusion of ions, making EDOT form a longer tubular fiber structure on the surface of the working electrode. Besides, with the participation of ionic liquid of BMIMTf2N, the PEDOT film (Figure 68A) shows larger porosity than other films which may be owing to the larger anion of BMIMTf2N. As shown in Figure 71, PEDOT:Ce@TiO2 film has a special nanostructure with "gully-like" rough surface morphology. The surface roughness, Ra of PEDOT:Ce@TiO2 measured by Atomic force microscopy (AFM) is 25.43 nm, which is significantly higher than that of PEDOT (Ra = 13.39 nm), indicating that

Ce@TiO2 has a significant influence on the surface morphology of PEDOT:Ce@TiO2. The difference between light and dark caused by the height difference cannot be observed in AFM phase diagram of PEDOT:Ce@TiO2 film (Figure 71f), which can be inferred that there is no obvious phase separation in this film.

As shown in Figure 72, PEDOT:Ce@TiO2 exhibits strong hydrophobicity while good wettability to acetonitrile solution. shows larger electrochemical activity compare to PEDOT as supercapacitor electrode materials. The mass specific capacitance of PEDOT:Ce@TiO2 film is 71.2 F/g at a current density of 1 A/g, which is 1.7 times higher than that of the PEDOT film. Poly-(EDOT-POT-1) was further tested as an electrode material for a supercapacitor in a three-electrode system using 0.1 M LiClO4/ACN as the electrolyte. As shown in

Conclusions

In conclusion, we developed new synthesis methods of organic monomers F-TH and TEPA. Thereafter, conjugated polymers such as P(F-TH), P(F-TH:EDOT), PTEPA and PEDOT were prepared. All of these polymers exhibit significant electrochromic

  Prof. Elena SAVINOVA, Université de Strasbourg Prof. Pierre MIALANE, Université de Saclay Prof. Fréderic LEMAITRE, Université PSL Paris Sciences et Lettre Dr. Pierre-Antoine BONNEFONT, Université de Strasbourg Dr. Sébastien BLANCHARD, Sorbonne Université I want to thank the Zhejiang Ai-shan Green and Technology Research Institute for its financial support throughout the study and live in France. I sincerely thank my supervisors for their advice, support and mentorship during my PhD. I sincerely thank Prof. Dr. Laurent RUHLMANN to carry out PhD at University of Strasbourg and giving me chance to work in his reseach group. I really enjoyed the scientific, academic, and friendly environment in his research group. His encouragement and personal care and advice were very important for me. I would also like to thank Prof. Dr. Pierre-Antoine BONNEFONT for his advice and suggestions which helped me to complete the thesis work on time. I need to thank Prof. Dr. Dominic S. Wright working in university of Cambridge, Prof. Dr. Cheng Zhang working in Zhejiang University of Technology, and my coworkers: Dr. Gang Liu (PhD student), Mr. Jun Chen (postgraduate student), Mr. Xing Yang (postgraduate student), Mr. Hu Wang (postgraduate student), Mr Cong-Ze Wang (postgraduate student) and Miss Yi-yao Shen, without their contributions, I can't complete my thesis on time.

  Au cours des travaux de recherche de cette thèse, nous avons conçu, synthétisé et caractérisé des séries de nouveaux matériaux à base de POT : matériaux composites TiO2/C ; matériaux composites CeTixOy/PEDOT (PEDOT : poly(3,4-éthylènedioxythiophène)) ainsi que des nouveaux matériaux copolymères Poly-(EDOT-POT) et Poly-(porphyrin-POT). Nous avons étudié les liens intrinsèques entre les microstructures et les propriétés électrochimiques de ces nouveaux matériaux.

Figure 1 .

 1 Figure 1. Structures des clusters du type POT syntétisés, A) [Ti2(OEt)9InI2], B) [Ti3O(O i Pr)9Cl], C) [Ti3CO2(O i Pr)10CoBr], D)

Figure 2 .

 2 Figure 2. a) Diffractogrames DRX des matériaux composites obtenus à partir de [Ti2O(OAc)2(HOAc)2Cl4]calciné à différentes températures [300 °C (K300), 400 °C (K400), 500 °C (K500), 600 °C (K600), 700 °C (K700), 800 °C (K800), 900 °C (K900), et 1000 °C (K1000)] dans l'air (22% de dioxygène et 78% de diazote); (b) Diffractogrames DRX des matériaux composites calcinés à différentes températures [300 °C (N300), 400 °C (N400), 500 °C (N500), 600 °C (N600), 700 °C (N700), 800 °C (N800), 900 °C (N900), et 1000 °C (N1000)] en présence uniquement de diazote.

Figure 1 ,

 1 Figure 1, TC = thiophène-3-carbonate, TA = thiophène-3-acétate). Par exemple, comme présenté sur la Figure 4, l'électropolymérisation de Ti6O6(TA)6(iPrO)6 (POT-1) en présence du 3,4-éthylènedioxythiophène (EDOT) permet d'obtenir un film 3D nanoporeux et stable (Poly-(EDOT-POT-1)). La morphologie du copolymère hybride conjugué Poly-(EDOT-POT-1) est uniquement influencée par le potentiel d'électropolymérisation

Figure 4 .Schéma 1 .

 41 Figure 4. A) Stratégie de copolymérisation utilisée pour obtenir des matériaux hybrides conjugués à partir du cluster POT-1 ; B) Structure RX à l'état solide du POT-1 (Ti6O6(TA)6(iPrO)6, TA = thiophène-3acétate). Les atomes H ont été omis pour plus de clarté (rouge = O, gris = C, vert = S, jaune = Ti) ; C) Spectres d'absorption UV-vis du polymère Poly-(EDOT-POT-1) à des tensions appliquées entre -0,8 V et 1,2 V dans une solution TBAH (0,1 M) / CH2Cl2 (les encarts sont les photographies des films polymères déposés sur électrode transparente du type ITO). D) Diagrammes de Nyquist (spectroscopie d'impédance électrochimique) des électrodes modifiées : PEDOT (courbe rouge) et Poly-(EDOT-POT-1) (courbe noire) mesurées dans une solution LiClO4 0,1 M + CH3CN à -0,156 V et -0,110 V respectivement. Les symboles représentent les données expérimentales et les lignes pleines les courbes simulées.

Figure 5 .

 5 Figure 5. Voltammogrammes cycliques enregistrés au cours de 25 premiers balayages itératifs effectués entre -1,50 V et +1,00 V / ECS en milieu NBu4PF6 0,1 mol.L -1 + 1,2-C2H4Cl2/CH3CN (7/3) avec ZnT2P (0,25 mmol.L -1 ) en présence de cluster POT-1 (0,25 mmol L -1 ). Electrode de travail : ITO. S = 1 cm 2 , v = 0,1 V s -1 . Courbe bleue : premier scan (n = 1). Courbe rouge : scan final (n = 25).

Figure 6 .

 6 Figure 6. Spectres d'absorption UV-visible-NIR de Poly-(H2T2P-POT-1) sur ITO avec différents nombres de balayages itératifs entre -1,50 et +1,00 V vs. SCE (v = 100 mV.s -1 ). Remarque : un seul côté de la plaque de verre est recouvert avec un film transparent conducteur du type ITO.

8 .

 8 photocourant en mode potentiostatique à 0 V sous des cycles d'éclairage marche-arrêt est représentée Figure 8. Sous illumination dans le domaine du visible, le potentiel de circuit ouvert augmente d'environ 40 mV. Au-dessus de ce potentiel, le courant d'oxydation I -devient prédominant du fait de la concentration élevée en ions I -en solution, empêchant ainsi une nouvelle augmentation du photopotentiel. Pour les potentiels inférieurs à l'OCP, un photocourant négatif est observé. Le photocourant à 0 V du film mince Poly-(H2T2P-POT-1) atteint -45 μA.cm -2 (expérience potentiostatique) ou -90 μA.cm -2 (mesuré à partir des voltamétrie cyclique). Les résultats des tests de photoélectrochimie indiquent que les films obtenus présentent de bonnes propriétés électrochimiques et photoélectrochimiques.

Figure 7 .Figure 8 .

 78 Figure 7. Courbes potentiel-courant des poly-(H2T2P-POT-1) films.

  matériaux composites TiO2/C peuvent être utilisés comme matériaux d'électrode pour batterie Li-ion et en qualité de supercondensateur en raison de leur excellente capacité de stockage d'énergie. Les matériaux composites CeTixOy/PEDOT et Poly-(EDOT-POT-1) préparés ont une forte surface hydrophobe et présentent des propriétés électrochromes prometteuses. Ces matériaux peuvent être utilisés dans des dispositifs électrochromes tels que les supercondensateurs électrochromes.

  photoluminescence, asymmetric catalysis and gas adsorption. Materials based on

Fourth, the carbon

  component in N800 can increased the conductivity of this composites which ensures rapid charge-discharge, and good rate performance. The aim of chapter IV is to develop new synthesis method for hybrid materials based on POT and CPs. CPs such as P(F-TH), P(F-TH:EDOT), PTEPA and PEDOT were prepared firstly (where P(F-TH) = poly(3-(N-trifluoroacétamido) thiophène), P(F-TH:EDOT) = poly(3-(N-trifluoroacétamido) thiophène-co-2,3-dihydrothieno-1,4dioxin), PTEPA = poly(tris[4-(3,4-ethylenedioxythiophene)phenyl]amine), and PEDOT = poly(2,3-dihydrothieno-1,4-dioxin)). These polymers exhibit significant electrochromic properties and have good electricity storage capacities. Furthermore, different POTs are incorporated into CPs and a series of inorganic/organic hybrid materials with improved electrochemical performances were obtained. Especially, Poly-(EDOT-POT-1) films have promising electrochromic properties and electricity storage capacities, this material can be used as electrode material in ECSC. Poly-(ZnT2P-POT-1) films exhibit good photocurrent generation behavior, which worth further study. In summary, this thesis reports design and synthesis of several new materials which were prepared based on POTs: TiO2/C composite materials can be used as electrode materials for Li-ion battery and supercapacitor because of their excellent energy storage capacity. CeTixOy/PEDOT composites and Poly-(EDOT-POT-1) have strong hydrophobic surface and exhibit promising electrochromic properties, these materials can be used in electrochromic devices such as electrochromic supercapacitor. Poly-(ZnT2P-POT-1) films exhibit good photocurrent generation behaviour, and the control of the thickness of the Poly-(ZnT2P-POT-1) films is of great importance to optimize the generation of photocurrent under visible illumination. As homogeneous hybrid materials, POTs grafting thiophene conjugate polymers are expected to solve or significantly decrease those problems caused by uneven dispersion and heterogeneity interfaces in conventional composite materials.

Figure 1 ,

 1 Figure 1, PEC devices can convert abundant solar energy directly into stored electric

Figure 1 .

 1 Figure 1. Schematic view of PEC devices. (Adapted from Ref. 6)

Figure 2 .

 2 Figure 2. Principles of four different applications of electrochromic devices. Arrows indicate incoming and outgoing electromagnetic radiation; the thickness of the arrows signifies radiation intensity. (Adapted from Ref. 25)

  Diverse synthetic methods open windows for the preparation of novel POTs with designed molecular structures and the engineering of their properties. So far, more than five hundred POTs' structures have been determined and documented. As shown in Figure 3, the nuclearity of POTs keeps growing from Ti3 to Ti52 [47-50]. In addition, diverse POT building blocks were successfully incorporated for the construction of extended frameworks, such as COK-69, MIL-91, MIL-125, MIL-125-NH2, MOF-901, MOF-902, NTU-9, PCN-22 and Ti-MIL-101 [51-53].

Figure 3 .

 3 Figure 3. Polyhedral views of recently reported high-nuclearity POTs: (a) [Ti13O10-(o-BDC)4(SAL)4(O i Pr)16], (b) Ti42 of TOF-1, (c) Ti52 of COM-3, and (d) [I@Ti22(μ-O)11(μ3-O)20(μ1-O i Pr)16(μ2-O i Pr)2( t BuCOO)9(OH2)H3] (I3)•HO i Pr. Alkoxide ligands are omitted for clarity. Atomic code: red, O; black, C. Polyhedral colour code: pink, TiO5; green, TiO6; yellow, TiO7. (Adapted from Ref. 50)

Figure 4 .

 4 Figure 4. (a) Microscope image of PCN-22 crystals; (b) structure of the Ti7O6 cluster (only O atoms of DEF molecules are shown for clarity); (c) representation of the tetratopic TCPP linker (left) and 12connected Ti7O6 cluster (right); (d) views of the structure of PCN-22 along a-axis and (e) b-axis. Color scheme: red O; black C; blue N; and cyan Ti. H atoms are omitted for clarity. (Adapted from Ref. 67)

shown in Figure 4 ,

 4 Zhou's group has used a photocatalytic POT, Ti6O6(O i Pr)6(ABZ)6

Figure 5 .

 5 Figure 5. Illustration of the ligand modification of phosphonate-stabilized [Ti6O4(O i Pr)10(O3PR)2] 2+ . (Adapted from Ref. 71)

Figure 6 . 1 . 6 . 3 Figure 7 ,

 61637 Figure 6. B3LYP functional method calculated projected density of states of (a) [MnTi14(OEt)28O14(OH)2], (b) [FeTi14(OEt)28O14(OH)2], (c) [GaTi14(OEt)28O14(OH)], (d) [Ti28MnKO37(OH)(OEt)40] and (e) [Ti27MnKO35(OH)2(OEt)39]. (Adapted from Ref. 56)

Figure 7 .

 7 Figure 7. Reaction scheme of POT cages [TixOy(OR)z] or M-POT cages [TixOy(OR)zMnXm] upon hydrolysis and further calcination, forming TiO2 or metal-doped TiO2 [M@TiO2]. The amorphous products initially formed probably consist of TiO2 mixed with organic residues. (Adapted from Ref. 42)

Figure 8 .

 8 Figure 8. Hypothesis of the mechanisms from POT (cage 1) to TiO2@C composites materials A and B. (Adapted from Ref. 85)

Figure 9 .

 9 Figure 9. Schematic illustration of the construction of inorganic-organic hybrid materials from POTs. (Adapted from Ref. 42)

Figure 10 .

 10 Figure 10. Schematic of the possible tethering mode POT of [Ti16O16(OEt)24{O(CH2)4SCH3}8] onto an Au surface. Blue = Ti, red = O, grey = C, yellow = S, orange = Au. The Au-S interactions are indicated by black arrows. (Adapted from Ref. 92)

  . The principle mechanism by which POTs mediate photocatalysis involves the photo-induced electron excitation of the TixOy core from the valence band [predominantly O(p)] to the conduction band [mainly Ti(d)]. After that, electrons and holes generated migrate to the surface of POT based materials where redox reactions occur. Usually, HOMO-LUMO gaps or band gaps of unmodified POTs and POT based materials are in the range of 3.5-4.0 eV, which means that electronic excitation from the valence band to conduction band requires ultraviolet photons with wavelength less than ca. 350 nm.Doping POT, especially metal doping POT, has proved to be effective in narrowing the band gaps via introducing additional energy levels within the band gap of the TixOy core. As shown in Figure11, functional ligand modification can be another important method for enhancing light absorption of POTs since functional ligands may act as photo-sensitizers that can harvest long wavelength photons and then transfered these photoexcited electrons to the TixOy core of POT[START_REF] Liu | Bandgap engineering of titanium-oxo clusters: labile surface sites used for ligand substitution and metal incorporation[END_REF][START_REF] Zhang | Visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT): an alternative approach to solar activation of titania[END_REF]. It is worth mentioning that isolated ligands not necessarily absorb at the same energy as the ligand modificated POT, because the ligand HOMO-LUMO can be mixed with the energy bands of the TixOy core upon bonding with POTs, which gives rise to a much narrower gap[START_REF] Chaumont | An unprecedented high nuclearity catecholato-based Ti (IV)-architecture bearing labile pyridine ligands[END_REF].

Figure 11 .

 11 Figure 11. The mechanism of photocatalytic reactions mediated by ligand modificated POTs: (1) excitation of a functional ligand, (2) and (3) electron transfer from the excited functional ligand to the POT core, (4) electron transfer to the photocatalytic reaction substrate, (5) electron-hole recombination, (6) ligand-to-metal charge transfer, (7) electron-hole recombination, (8) hole transfer to the photocatalytic reaction substrate. (Adapted from Ref. 42)

Figure 12 .

 12 Figure 12. (a) POT molecular structure of [Ti13O10(o-BDC)4(SAL)4(O i Pr)16], blue = Ti, red = O, grey = C, hydrogen atoms are omitted for clarity. 6 is isostructural with 5, except that the -OH ortho hydrogen atoms are substituted by chlorine in four out of the six salicylate ligands; (b) photocurrent responses of the films of 5 and 6 on ITO upon cycling the irradiation. (Adapted from Ref. 95)

) 20 (

 20 photocurrent of Co-and Fe-doped POTs compared with Cd-and Mn-doped POT is

Figure 13 .Figure 14 ,

 1314 Figure 13. SEM images of the deposited films from: (a) and (b) [Ti17O28(O i Pr)16(CoPhen)2] (Adapted from Ref. 96)

Figure 14 .

 14 Figure 14. (a) Solid-state structure of [Ti6O4(o-BDC)2(o-BDC-i Pr)2(O i Pr)10], blue = Ti, red = O, grey = C, hydrogen atoms are omitted for clarity; optical microscope images of crystalline blocks of [Ti6O4(o-BDC)2(o-BDC-i Pr)2(O i Pr)10] before (b) and after (c) irradiation; (d) UV-Vis spectra of an analogous photochromic L-POT [Ti6O3(o-BDC)2(O i Pr)14] before and after irradiation. (Adapted from Ref. 100)

Figure 15 .

 15 Figure 15. (a) Molecular structure of the tetranuclear [Ti4(μ3-OH)4(R-BINOLato)6], the S-BINOL enantiomer structure has a similar configuration (not shown); (b) molecular representation of 7,7′substituted [Ti4(μ3-OH)4(7,7′-di-R-BINOLato)6] cage; (c) illustration of the steric reason for the favorable production of (3R,5S) over (3S,5R) products. (Adapted from Ref. 110)

Figure 16 . 1 . 7

 1617 Figure 16. POTs' structures of (a) [Ti6O6(abz)6(O i Pr)6] and (b) [Ti8O10(abz)12] (abz = aminobenzoate), blue = Ti, red = O, blue = N, grey = C, hydrogen atoms are omitted for clarity. Gas-sorption isotherms measured for compound (c) [Ti6O6(abz)6(O i Pr)6] and (d) [Ti8O10(abz)12]; inset of (c) is the isotherms of [Ti6O6(abz)6(O i Pr)6] with complete crystalline disruption; filled and open symbols denote adsorption and desorption, respectively. (Adapted from Ref. 116)

  allows the temperature of reactions above the boiling point of organic solution. As shown in Figure 17, autoclaves for solvothermal reactions are hermitically sealed steel vessels with Teflon inner cylinder which could withstand high temperatures and pressures for long durations. The chemically inert cylinder must not take part in the solvothermal process. Crystal data were collected on a Bruker D8 VENTURE diffractometer using Mo(Kα) radiation (λ = 0.71073 Å). The structures were solved by Direct Methods and refined by full-matrix least squares on F 2 [117]. Infrared (IR) spectra were adopted using a Nicolet 6700 spectrometer (Thermo Fisher Nicolet, USA) with KBr pellets. Powder Xray diffraction (pXRD) experiments were performed using a X'Pert Pro diffractometer with Cu-Kα radiation (λ= 1.5418Å) operating at 40 kV and 40 mA and the scanning angle ranged from 5° to 50° of 2θ. Proton ( 1 H) nuclear magnetic resonance (NMR) spectra were measured in chloroform-d (CDCl3) using Bruker AVANCE III 500 MHz spectrometers. ESI-MS was carried out on ThermoFisher LCQ TM Deca XP plus. UVvis spectra were obtained using a UV-1800 spectrophotometer (SHIMADZU), and visible and NIR transmission spectra was performed in 0.1 mol/L TBAPF6/DCM solution. Thermogravimetric (TG) analyses were performed on a Mettler Toledo TGA/DSC 1 under nitrogen atmosphere. The crystals of POT-1, POT-2, and POT-3 was firstly obtained by one of my author coworkers: Dr. Gang Liu in Prof. Cheng Zhang's Lab of Zhejiang University of Technology; the crystals of POT-4 was firstly obtained by my anthor coworkers: Mr. Xing Yang in Prof. Cheng Zhang's Lab of Zhejiang University of Technology; POT-5, POT-6, POT-7, POT-8, POT-9, POT-10, POT-11 were strucutally determined in Univeristy of Cambridge with the help of Prof. Dominic S. Wright.

Figure 17 .

 17 Figure 17. A schematic description and a photographic view of the autoclave used in the present study for solvothermal synthesis for POTs.

Figure 18 .

 18 Figure 18. The 1 H NMR of POT-1 in CDCl3.

Figure 19 .

 19 Figure 19. (a) ESI-MS spectrum of POT-1 in CDCl3 solution. The sample were dissolved and kept in CDCl3 before MS analysis, which was diluted by ACN and immediately before injected into the MS instrument; (b) Zoomed image of the spectrum peaks around 1584.9; (c) Simulation of the pattern for [M+H] + ; (d) Zoomed image of the spectrum peaks around 1606.9 for [M+Na] + ; (e) Zoom of the spectrum peaks around 1622.9 for [M+K] + .

Figure 20 .Figure 21 .

 2021 Figure 20. X-ray Powder Diffraction (pXRD) of POT-1.

Figure 22 .

 22 Figure 22. (A) Solid-state structure of POT-1, H-atoms have been omitted for clarity (red = O, gray = C, green = S, yellow = Ti); (B) Photographic image of crystals of POT-1.

23 .

 23 80 o C for 2 days, colorless crystals of Ti3O5(O i Pr)8(TC)2 (POT-2) were obtained by cooling to room temperature, yield 0.20g (21 % with respect to Ti supplied). The infrared spectrum of POT-2 is shown in Figure As shown in Figure 24, sXRD analysis shows that POT-2 contains a Ti3O core. A Ti(IV) centre have a six-coordinate, octahedral geometry, being bonded to a μ3-O oxoatom within the core, two O atoms from two TC ligands (TC = thiophene-3-carboxilic acid) and three isopropoxide-O atoms, another six-coordinate Ti(IV) centre also displays octahedral geometry, being bonded to a μ3-O oxo-atom within the core, a O atoms from one TC ligand and four isopropoxide-O atoms, the rest five-coordinate Ti(IV) centre displays triangular bipyramid geometry, being bonded to a μ3-O oxoatom within the core, a O atoms from one TC ligand and three isopropoxide-O atoms.

Figure 23 .

 23 Figure 23. Infrared spectrum of monomer POT-2.

Figure 24 .

 24 Figure 24. Solid-state structure of POT-2, H-atoms have been omitted for clarity (red = O, gray = C, green = S, yellow = Ti).

2. 2 . 4

 24 Synthesis and Characterisation of [Ti3O5(O i Pr)8(PC)2] (POT-3).Titanium isopropoxide (1 ml, 4.8 mmol), Pyrrole-3-carboxylic acid (PCH) (0.12 g, 1.0 mmol) and isopropyl alcohol (4.5 ml) were mixed in a glass bottle and heated at 80 o C for 2 days, colorless crystals of Ti3O5(O i Pr)8(PC)2 (POT-3) were obtained by cooling to room temperature, yield 0.25g (30 % with respect to Ti supplied). The infrared spectrum of POT-3 is shown in Figure25.

Figure 25 . 3 . 2 ,

 2532 Figure 25. Infrared spectrum of monomer POT-3.

Figure 26 .

 26 Figure 26. Solid-state structure of POT-3, H-atoms have been omitted for clarity (red = O, gray = C, blue = N, yellow = Ti).

2. 2 . 5 4 .

 254 Synthesis and Characterisation of [Ti4O6(O i Pr)10(TC)2] (POT-4).Titanium isopropoxide (1 ml, 4.8 mmol), Thiophene-3-carboxylic acid (TCH) (0.13 g, 1.0 mmol), cobalt bromide hexahydrate 0.176 g (0.54 mmol) and anhydrous acetonitrile (6.0 ml) were mixed in a glass bottle and heated at 80 o C for 3 days, colourless crystals of Ti4O6(O i Pr)10(TC)2 (POT-4) were obtained by cooling to room temperature, yield 0.23g (22 % with respect to Ti supplied). As shown in Figure 27, sXRD analysis shows that POT-4 contains a Ti4O2 core with 4 Ti(IV) centers, a μ4-O oxo-atom and a μ2-O oxo-atom. Each Ti(IV) centre have a six-coordinate, octahedral geometry. The sXRD data and refinement of POT-4 are summarized and shown in Table Selected bond lengths (Å) and angles ( o ) of POT-4 are shown in Table

Figure 27 .

 27 Figure 27. Solid-state structure of POT-4, H-atoms have been omitted for clarity (red = O, gray = C, green = S, yellow = Ti).

Figure 28 .

 28 Figure 28. Solid-state structures of POT-5. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, green = Cl, yellow = Ti).

Figure 29 .

 29 Figure 29. Solid-state structures of POT-6. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, pink = I, blue = In, yellow = Ti).

  and the mixture heated to 150 o C for 3 days. Colourless crystals of [Ti3O(O i Pr)9Cl] (POT-7) were obtained by cooling to room temperature. As shown in Figure 30, sXRD analysis shows that POT-7 contains a Ti3O4Cl core, each of Ti(IV) centre is six-coordinated octahedral geometry, being bonded with a μ3-O oxo-atom and a μ3-Cl atom within the core, two bridging isopropoxide ligands and two terminal isopropoxide ligands. Interestingly, there is a μ3-Cl atom in the core of POT-7, which is very rare. Structure solutions and refinements details of POT-7 are listed in

Figure 30 .

 30 Figure 30. Solid-state structures of POT-7. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, green = Cl, yellow = Ti).

8 .

 8 and the mixture heated to 150 o C for 3 days, the obtained blue solution were futher placed in -15 o C, violet crystals of [Ti3O(CO3 i Pr)(O i Pr)10CoBr] (POT-8) were obtained in two weeks. As shown in Figure 31, sXRD analysis shows that POT-8 contains a Ti3CoO6 core, containing two six-coordinated Ti(IV) centres, one five-coordinated Ti(IV) centre and one five-coordinated Co(II) centre. Each six-coordinated Ti(IV) centre exhibits octahedral geometry, being bonded with a μ4-O oxo-atom, three bridging isopropoxide ligands and a terminal isopropoxide ligands, a O atom from isopropyl carbonate (CO3 i Pr) ligand. The five-coordinated Ti(IV) centres shows distorted trigonal bipyramidal geometry, being bonded with a μ4-O oxo-atom, two bridging isopropoxide ligands and two terminal isopropoxide ligands, The five-coordinated Co(II) centre also shows distorted trigonal bipyramidal geometry, being bonded with a μ4-O oxo-atom, three bridging isopropoxide ligands and a terminal bromide ligand. Interestingly, the isopropyl carbonate (CO3 i Pr) ligand is not belong to starting chemical but probably derived from in situ oxidation of isopropanol during slovothermal synthesis of POT-Structure solutions and refinements details of POT-8 are listed in Table 8, selected bond lengths (Å) and angles ( o ) of POT-8 are shown in Table

Figure 31 .

 31 Figure 31. Solid-state structures of POT-8. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, blue = Co, violet = Br, yellow = Ti).

2. 2 .

 2 10 Synthesis and Structure of [Ti4O2(O i Pr)14CeCl2] (POT-9). Titanium isopropoxide (2 ml, 9.54 mmol), cerium chloride anhydrous (0.246g, 1.0 mmol) and isopropanol anhydrous (7 ml) was placed in an autoclave under nitrogen and the mixture heated to 150 o C for 3 days, the obtained orange solution was futher placed in room temperature, violet crystals of [Ti4O2(O i Pr)14CeCl2] (POT-9) were obtained by cooling in three weeks. Yield 0.58g 27%. As shown in Figure 32, sXRD analysis shows that POT-9 contains a Ti4O6CeCl2 core, containing four six-coordinated Ti(IV) centres and a eight-coordinated Ce(III) centre. Each six-coordinated Ti(IV) centre exhibits octahedral geometry, being bonded with a μ3-O oxo-atom, three bridging isopropoxide ligands, a terminal isopropoxide ligands and a μ3-O chloride ligand. The eight-coordinated Ce(III) centre exhibits dodecahedron geometry, being bonded with two μ4-O oxo-atom, two μ3-O chloride ligands, and four bridging isopropoxide ligands. Structure solutions and refinements details of POT-9

Figure 32 .

 32 Figure 32. Solid-state structures of POT-9. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, blue = Ce, green = Cl, yellow = Ti).

Figure 33 .

 33 Figure 33. Solid-state structures of POT-10. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, blue = Cu, yellow = Ti).

POT- 11 .

 11 More interesting is the anionic [(ICo)6Ti15O24(O i Pr)18(I)] -host-guest assembly of This is composed of a neutral nearly D3-symmetric heterometallic Co6Ti15O42 cage in which the six tetrahedral Co II ions are coordinated at its periphery within dimeric subunits. The Ti15O24 core of the anion forms an approximately spherical shell with an internal diameter of ca.8 Å, in which each of the Ti centres bonded to four equatorial oxo-atoms of the shell and an axial isopropoxide group and have chemically similar square-based pyramidal geometries. The remarkable feature of the anion is the apparent weakness of the bonding of the encapsulated iodide ion to the internal shell surface. Structure solutions and refinements details of POT-11 are listed in Table 11, selected bond lengths (Å) and angles ( o ) of POT-11 are shown in Table

Figure 34 .

 34 Figure 34. Solid-state structures of POT-11. H-atoms (which could not be located from X-ray data) have been omitted for clarity (red = O, gray = C, blue = Co, pink = I, yellow = Ti).

  crystals of [Ti8O7(HOEt)(OEt)21Ce] (POT-12) were obtained through the slovothermal reaction of the mixture containing tetraethyl titanate (3.5 mL, 15.4 mmol), anhydrous cerium chloride (0.246g, 1 mmol) and anhydrous ethanol (7 mL) into the autoclave. the mixture heated to 150 o C for 2 days gave a light yellow solution, and orange crystals of POT-12 were obtained from the yellow solution through slowly evaporate the solvent at room temperature. The synthesis and structure of POT-12 were reported in 2013 [116d]. Herein, we used POT-12 as a precursor to prepare new hybrid material.

2. 3 Conclusions

 3 In summary, twelve different POTs with different formula and structure have been successfully synthesized and structural determined. In these POTs, there are functional ligands modified POTs like POT-1, POT-2, POT-3, POT-4 and metal doped POTs like POT-6, POT-8, POT-9, POT-10, POT-11, which obtained via different synthesis method. The cost of synthesizing large amounts of POT-5 is relatively low, thus we further studied the preparation and application of a serious of TiO2@C materials through calcination of POT-TiO2 based materials, which have been widely used in photocatalysis, sensors, solar cells, lithium-ion batteries and other fields, are important candidates for anode materials of lithium-ion battery. These materials have many advantages, such as has easy-to-obtain, long charge-discharge cycle life, environmental friendly and small volume changes during charging and discharging process [119-123]. Compared with carbon materials, TiO2 has a high charge and discharge platform (~1.5 V) which can avoid the generation of SEI (Solid Electrolyte Interface) film and lithium dendrites [124,125], but its disadvantages (e.g. wide band gap, poor conductivity, low specific capacity and so on) limit its commercialization in electrode materials of battery [126,127].Through introducing nanoporous into TiO2, the transmission of electrons and lithium ions can be effectively improved[128][129][130][131][132][133]. In addition, another effective modification method is to combine TiO2 with highly conductive materials and fabricate composites. For instance, the conductivity of titanium dioxide can be significantly improved after combination with carbon-based materials, and their rate performance will be further improved[134][135][136][137][138].

  hours at 300 o C, 400 o C, 500 o C, 600 o C, 700 o C, 800 o C, 900 o C or 1000 o C, respectively. Nanoporous C@TiO2 named K300, K400, K500, K600, K700, K800, K900, K1000 were obtained. Calcination of the crystals of POT-5 in a nitrogen flow for 5 hours at 300 o C, 400 o C, 500 o C, 600 o C, 700 o C, 800 o C, 900 o C or 1000 o C,

Figure 35 .Figure 35

 3535 Figure 35. (a) XRD patterns about C@TiO2 materials of K300, K400, K500, K600, K700, K800, K900, K1000, (b) XRD patterns about C@TiO2 materials of N300, N400, N500, N600, N700, N800, N900, N1000.

Figure 39 .

 39 Figure 39. particle size distribution curve of (a) K500 and N500, (b) K600 and N600, (c) K800 and N800, (d) K900 and N900.

Figure 40 .

 40 Figure 40. Nitrogen adsorption and desorption isotherms about (a) K500, K600, K800, K900 and (b) N500, N600, N800, N900.

Figure 41 .

 41 Figure 41. Pore size distribution curves of (a) K500, K600, K800, K900 and (b) N500, N600, N800, N900.

42 .

 42 5 mV/s and voltage range from 0 to 3 V are shown in Figure All of these C@TiO2 composite materials have a pair of redox peaks around 2.10 V and 1.68 V, corresponding to the reversible process of lithium extraction/intercalation in the material.

Figure 42 .

 42 Figure 42. CV curves of (a) K500, K600, K800, K900, (b) N500, N600, N800, N900.

Figure 43b ,

 43b Figure 43b, the first discharge specific capacities of materials N500, N600, N800 and

Figure 43 .

 43 Figure 43. first cycle of galvanostatic charge-discharge curves at current density of 50 mA/g about (a) K500, K600, K800, K900, (b) N500, N600, N800, N900.

Figure 44 .

 44 Figure 44. Rate capability diagrams of (a) K500, K600, K800, K900 and (b) N500, N600, N800, N900 at different current densities, cycling stability of (c) K500, K600, K800, K900 and (d) N500, N600, N800, N900.

Figure 45 .

 45 Figure 45. Nyquist plots of (a) K500, K600, K800, K900 and (b) N500, N600, N800, N900.

Chapter 4 Hybrid materials based on POTs and conjugated polymers 4 . 1 Introduction

 441 The electrochromic devices (ECDs) such as electrochromic smart windows, which can efficiently adjust light transmission through reversible color and transparency changes under an external voltage, and supercapacitors (SCs), which are advanced electrochemical energy storage devices characterised for their high power density and short charging times, have similar working mechanisms and device structures. As a result, there is the interesting prospect of the integrating energy storage and electrochromic functions into one device. As a promising smart device, such electrochromic supercapacitors (ECSCs) have attracted considerable interest over the past decade [139-144]. In comparison with traditional ECDs, ECSCs not only have the function of energy storage, but also can act simultaneously as a smart energy monitor, indicating the state of energy storage capacity through color changes. In addition, ECSCs are also expected to overcome problems concerning external power sources and the limited range of application of conventional ECDs. Good electrode materials are one of the key problems for the development of ECSCs. In general, bare materials or inorganic materials have many defects. The use of organic-inorganic hybrid materials has gradually become our focus.Conjugated polymers have been widely viewed as an attractive option for electrode materials due to their adjustable band gaps, large theoretical specific capacitances, good electrical conductivity, high elemental abundance, light weight, and tunable mechanical flexibility. On the other hand, there has been considerable interest in POTs, which possess well-defined inorganic TixOy cores surrounded by organic ligands. Recently, POTs have proved to be particular effective precursors for formation of various titania composites, with controlled composition and morphology.

(

  Shanghai) companies. Ltd., and were used without further purification. Indium tin oxide (ITO)-coated glass (sheet resistance Rs ≤ 10 Ω) was purchased from Guluo Glass Technology Co. Ltd. It was ultrasonically washed in deionized water, ethanol, acetone, toluene and (finally) ethanol solutions. Proton ( 1 H) nuclear magnetic resonance (NMR) spectra were recorded with a Bruker Avance III instrument (Bruker, Switzerland) at 500 MHz. Fourier transform infrared (FT-IR) spectra were obtained using a Nicolet 6700 spectrometer (Thermo Fisher Nicolet, USA). Extracted ion chromatogram and mass spectra (MS) were explored using a ABSCIEX HPLC-TripleTOF 5600 Mass Spectrometer. Elemental analysis was obtained using a Perkin-Elmer 4200 elemental analyzer. Powder X-ray diffraction (pXRD) experiments were performed using a X'Pert Pro diffractometer with Cu-Kα radiation (λ= 1.5418 Å) operating at 40 kV and 40 mA and a scanning angle ranging from 5° to 50° of 2θ.

F3_1Figure 46 .

 46 Figure 46. Molecular structure of F-TH with partial atom numbering scheme, H-atoms have been omitted for clarity (red = O, blue = N, gray = C, green = F, yellow = S), only one of the three independent molecules in the unit cell is shown.

Figure 47 .

 47 Figure 47. Molecular structure of F-TH with partial atom numbering scheme, H-atoms have been omitted for clarity (red = O, blue = N, gray = C, green = F, yellow = S), only one of the three independent molecules in the unit cell is shown.

  unoccupied molecular orbitals (LUMO) computed at the B3LYP/6-311+G(d, p) level for the molecules of F-TH, thiophene and 3,4-ethylenedioxythiophene (EDOT) are illustrated in Figure 48. Calculation results indicate that the F-TH molecule has 49 occupied molecular orbitals (MOs), much more complicated in comparison with that of thiophene (22 occupied MOs) and EDOT (37 occupied MOs). The DFT calculations results of the HOMO level, LUMO level and HOMO-LUMO energy gap (Eg) of F-TH and EDOT are presented in Table16. In these molecules, both the HOMOs and LUMOs are mostly π-antibonding type orbitals, F-TH has lower HOMO and LUMO levels than that of thiophene and EDOT. HOMO-LUMO energy separation has been used as a simple indicator of kinetic stability [148,149], the calculated Eg of F-TH is 5.98 eV, which is a bit smaller than Eg of thiophene (5.99 eV), and is larger than Eg of EDOT (5.61 eV) owing to strong electron-withdrawing ability of CF3 group. These calculation results imply that F-TH may exhibit lower kinetic stability and higher chemical reactivity compared with EDOT.

Figure 48 .

 48 Figure 48. Molecular orbital surfaces and energies for the HOMO and LUMO of EDOT, F-TH and thiophene.

4. 2 . 2 . 2

 222 Synthesis of tris[4-(3,4-ethylenedioxythiophene)phenyl]amine (TEPA) As shown in Figure 49, the TEPA (tris[4-(3,4-ethylenedioxythiophene)phenyl]amine) monomer was obtained via a four-step synthetic route using EDOT and triphenylamine TPA (triphenylamine) as the starting materials in an overall yield of 55%.

Figure 49 .

 49 Figure 49. The new synthetic route for the TEPA monomer.

Figure 50 . 1 H

 501 Figure 50. 1 H NMR (CDCl3, 400 MHz) spectrum of TEPA monomer.

Figure 51 .Figure 52 .

 5152 Figure 51. The FT-IR spectra of TEPA.

Figure 53 ,

 53 molecules of TEPA have a propeller-like TPA core with each 'blade' being an EDOT group and with the central N-atom being nearly trigonal planar [C-N-C over the three independent molecules being in the range of 118.5(10)-122.2(9) o ]. The carbon atoms at the 2-position of the thiophene rings of the EDOT groups are bonded to the para position of the triphenylamine groups of the TPA core. As shown in Figure 54, C-H•••O intermolecular hydrogen bonds connect adjacent molecules and form two-dimensional layers within the lattice, which further extend into a 3D supramolecular structure through Van der Waals interactions (Figure 55).

Figure 53 .

 53 Figure 53. Molecular structure of TEPA, H-atoms have been omitted for clarity (red = O, blue = N, gray = C, yellow = S), and only one of the three independent molecules in the unit cell is shown.

Figure 54 .

 54 Figure 54. Two-dimensional layers of TEPA molecules linked by C-H•••O intermolecular hydrogen bonds.

Figure 55 .

 55 Figure 55. Molecular packing of TEPA.

Figure 56 .

 56 Figure 56. Key dimensions of the TEPA monomer units, indicating the distortion of the polymer building blocks.

Figure 57 .

 57 Figure 57. (a) Schematic representation of the TEPA monomer as a building block, (b) two possible assemblies of PTEPA, (c) a possible spiral channel of PTEPA, (d) a possible porous polymer structure of PTEPA.

Figure 58 .

 58 Figure 58. Optical absorption spectrum of P(F-TH) under different potentials (-0.6~0.6V).

Figure 59 .

 59 Figure 59. SEM images of PEDOT taken at a magnification of (a) 25k and (b) 100k; SEM images of P(F-TH:EDOT) taken at a magnification of (c) 25k and (d) 100k.

Figure 60 .

 60 Figure 60. Water droplet contact angles of (a) PEDOT and (b) P(F-TH:EDOT), CH3CN droplet contact angle of (c) PEDOT and (d) P(F-TH:EDOT).

Figure 61 .

 61 Figure 61. (a) CV curves of the P(F-TH:EDOT) (red) and PEDOT (black) at a scan rate of 50 mV•s -1 in 0.1 mol•L -1 LiClO4/CH3CN solution; (b) CV curves of the P(F-TH:EDOT) at different scan rate in 0.1 mol•L -1 LiClO4/CH3CN solution and plots of the peak currents in different scan rate (insert).

Figure 62 .

 62 Figure 62. (a) Nyquist plots of the impedance spectra of P(F-TH:EDOT) (red) and PEDOT (black) modified electrodes measured in 0.1 mol•L -1 LiClO4/CH3CN, (b) Equivalent circuit used to fit the spectra.

Figure 63 .

 63 Figure 63. Spectroelectrochemical spectra of (a) PEDOT and (b) P(F-TH:EDOT) with different applied potentials between -0.8 V and 0.8 V.

Figure 64 . 4 . 2 . 3 . 2

 644232 Figure 64. The simultaneous monitoring of (a) transmittance and (b) switching current for P(F-TH:EDOT) film (green) monitored at 616 nm and PEDOT film (blue) monitored at 620 nm, switching response for (c) P(F-TH:EDOT) and (d) PEDOT films monitored at corresponding wavelengths in 0.1 mol•L -1 LiClO4/CH3CN solution between their neutral (-0.8 V) and oxidized (0.8 V) states at 5 s intervals.

Figure 65 .Figure 66c .

 6566c Figure 65. SEM images of PTEPA powder taken at a magnification of (a) 20k and (b) 60k; (c) SEM image of a PTEPA film; (d) Nitrogen adsorption-desorption isotherms of PTEPA powder; (e) BJH pore size distribution from the desorption isotherms of PTEPA; (f) microporous pore size distribution in PTEPA calculated from the adsorption isotherms.

Figure 66 .

 66 Figure 66. (a) CV curve of the PTEPA electrode in LiPF6 EC/DMC (v/v, 1:1) electrolyte versus Li/Li + , at a scan rate of 1 mV/s; (b) Initial charge-discharge curves of the PTEPA electrode at a current density of 20 mA/g; (c) Cycling stability of the PTEPA electrode at a current density of 20 mA/g; (d) Coulombic Efficiency of the PTEPA electrode; (e) CV curve of the PTEPA film in 1 mol/L H2SO4 aqueous solution versus Ag/AgCl, at a scan rate of 100 mV/s (f) GCD curves of the PTEPA film in 1 mol/L H2SO4 aqueous solution at approximately 10 A/g.

Figure 67 . 4 . 2 . 3 . 3

 674233 Figure 67. (a) Spectroelectrochemical spectra of PTEPA films with different applied potentials between -0.4 V and 1.0 V; (b) Transmittance-time profiles of PTEPA films at 440 nm and 660 nm between -0.4 and 1.0 V with a residence of 5 s; (c) Switching response for PTEPA films monitored at 440 nm; (d) Switching response for PTEPA films monitored at 660 nm.

Figure 68 .

 68 Figure 68. SEM images of PEDOT films grown in the solvent of DCM (A,C,E,G,I,K) and ACN (B,D,F,H,J,L) with the electrolyte of 0.1mol/L BMIMTf2N (A, B); BMIMBF4 (C, D); TEATFB (E, F); TEAPF6 (G, H); TBAPF6 (I, J) and TBAP (K, L).

Figure 69 .Figure 68 , 4 . 2 . 4 Hybrid materials based on POTs and conjugated polymers 4 . 2 . 4 . 1 12 [

 6968424424112 Figure 69. Water droplet contact angles of PEDOT films prepared in the solvent of ACN (e-h) or DCM (a-d) with 0.1 mol/L BMIMTf2N (a, e); BMIMBF4 (b, f); TEATFB (c, g) and TEAPF6 (d, h).

Figure 70 . 3 .

 703 Figure 70. Schematic illustration of preparation of PEDOT:Ce@TiO2 film.

Figure 71 .

 71 Figure 71. (a) SEM image, (b) AFM height sensor image, (c) AFM tapping phase image of PEDOT film; (d) SEM image, (e) AFM height sensor image, (f) AFM tapping phase image of PEDOT:Ce@TiO2 film.

Figure 72 .

 72 Figure 72. Images of water droplets on the surfaces of (a) PEDOT film and (c) PEDOT:Ce@TiO2 film; Images of ACN droplets on the surfaces of (b) PEDOT film and (d) PEDOT:Ce@TiO2 film.

Figure 73 .

 73 Figure 73. UV-Vis spectra and optical photos (insert) of films under different potential, (a) PEDOT, (b) PEDOT:Ce@TiO2.

Figure 74 . 4 . 2 . 4 . 2 4 )

 7442424 Figure 74. CV curves of (a) PEDOT and (b) PEDOT:Ce@TiO2, galvanostatic charge/discharge curves of (c) PEDOT and (d) PEDOT:Ce@TiO2.

Figure 75 . 4 )POT- 4 ) 4 . 2 . 4 . 3 1 )Figure 77 .

 75444243177 Figure 75. CV curves of PTEPA and Poly-(TEPA-POT-4) films in 0.1 mol•L -1 TBAPF6/DCM at scan rate of 100 mV•s -1 .

Figure 78 . 78 ,

 7878 Figure 78. SEM and elemental mapping of plane (A) and section (B) of the Poly-(EDOT-POT-1) film.

Figure 79 .

 79 Figure 79. CV curves of Poly-(EDOT-POT-1) and PEDOT films on the surface of the glassy carbon electrode in 0.1 mol/L TBAPF6/DCM at scan rate of 10 mV/s.

Figure 80 .

 80 Figure 80. UV-vis spectra of (A) Poly-(EDOT-POT-1) and (B) PEDOT at applied voltages between -0.8 V and 1.2 V in 0.1 M TBAH/DCM solution (insets are the photographs of the corresponding polymer films on ITO glass).

Figure 81 .

 81 Figure 81. Optical contrast of the Poly-(EDOT-POT-1) (red curve) polymer films monitored between -0.5 V and 0.7 V and the PEDOT (black curve) films monitored between -0.5 V and 0.8 V in 0.1 M TBAH/DCM solution with a residence time of 10 s (A); Electrochromic switching response of Poly-(EDOT-POT-1) (B) and PEDOT (C).

Figure 82 ,

 82 Figure 82, CV curves of Poly-(EDOT-POT-1) and PEDOT both exhibit a quasi-

Figure 82 .

 82 Figure 82. CV curves of PEDOT (A) and Poly-(EDOT-POT-1) (B); galvanostatic charge/discharge curves of PEDOT (C) and Poly-(EDOT-POT-1) (D).

Figure 83 .

 83 Figure 83. Nyquist plots of the impedance spectra of PEDOT (red) and Poly-(EDOT-POT-1) (black)

4. 2 . 4 . 4 1 )

 2441 photocurrent generation.

Figure 85 .

 85 Figure 85. UV-visible-NIR absorption spectra of Poly-(H2T2P-POT-1) onto ITO with different numbers of iterative scans between -1.50 and +1.00 V vs. SCE ( v=100 mVs -1 ). Only one side is covered by ITO.

Figure 86

 86 Figure 86 shows the typical current-potential curves of Poly-(H2T2P-POT-1) thin films on ITO electrodes obtained in 5 mM I2/0.5 M I -aqueous solution. The

Figure 86 .

 86 Figure 86. Potential-current curves of Poly-(H2T2P-POT-1) films measured in the dark or under visible illumination using 300 W arc Xenon lamp and a long pass filter ( > 400 nm).

Figure 87 .

 87 Figure 87. Photoelectrochemical response of Poly-(H2T2P-POT-1) films obtained with various iterative scans.

4 . 5 . 2 Scope of Further Work 1 . 1 ) 2 .

 452112 properties and have good electricity storage capacities. We further introduced different POTs into conjugated polymers and obtain a series of inorganic/organic hybrid materials which have improved electrochemical performances. Especially, Poly-(EDOT-POT-1) films have promising electrochromic properties and electricity storage capacities, this material can be used as electrode material in ECSC. Preliminary results presented at the end of this chapter have shown that hybrid free base porphyrin/POT copolymer, namely Poly-(H2T2P-POT-1) can be prepared from zinc 5,15-ditolylporphyrin and POT-1 subunits. Poly-(H2T2P-POT-1) films exhibit good photocurrent generation behavior. It will be a good candidate for the development of photovoltaic devices. with implications to a range of existing functional organic polymers. Poly-(H2T2P-POT-1) films exhibit good photocurrent generation behavior, and the control of the thickness of the Poly-(H2T2P-POT-1) films is of great importance to optimize the generation of photocurrent under visible illumination. The synthesis method of Poly-(H2T2P-POT-1) films could be further improved. The mechanism of the electropolymerization needs further investigation. The photo-electrochemistry properties of Poly-(H2T2P-POTwill be fully studied in future. the overall conversion efficiency η of the sealed cell using Poly-(H2T2P-POT-1) as electrode materials also to be studied. Although we have explored the incorporation of the polymerizable ligand into POTs. Till now we only obtain 4 polymerizable POTs monomers. We will try to obtain more POTs monomers especially heterometallic POTs monomers in future. 3. As homogeneous hybrid materials, POTs grafting conjugate polymers are expected to solve or significantly decrease those problems caused by uneven dispersion and heterogeneity interfaces in conventional composite materials. More experiments are waiting for us to prove the advantages of this kind of hybrid matrials. orbital calculations. Journal of the American Chemical Society, 126(46), 15295-15308. 152. Poverenov, E., Sheynin, Y., Zamoshchik, N., Patra, A., Leitus, G., Perepichka, I. F., & Bendikov, M. (2012). Flat conjugated polymers combining a relatively low HOMO energy level and band gap: polyselenophenes versus polythiophenes. Journal of Materials Chemistry, 22(29), 14645-14655. 153. Hwang, H., Kim, Y., Kang, M., Lee, M. H., Heo, Y. J., & Kim, D. Y. (2017). A conjugated polymer with high planarity and extended π-electron delocalization via a quinoid structure prepared by short synthetic steps. Polymer Chemistry, 8(2), 361-365. 154. Wijsboom, Y. H., Patra, A., Zade, S. S., Sheynin, Y., Li, M., Shimon, L. J., & Bendikov, M. (2009). Controlling Rigidity and Planarity in Conjugated Polymers: Poly (3, 4-ethylenedithioselenophene). Angewandte Chemie, 121(30), 5551-5555. 155. Chen, Z., Li, W., Dai, Y., Xu, N., Su, C., Liu, J., & Zhang, C. (2018). Conjugated microporous polymer based on star-shaped triphenylaminebenzene structure with improved electrochemical performances as the organic cathode material of Li-ion battery. Electrochimica Acta, 286, 187-194. 156. Su, C., Yang, F., Ye, Y., Xu, L., Wang, L., & Zhang, C. (2013). Poly [tris (thienylphenyl) amine] derivatives as a performance-improved cathode material for lithium ion batteries. Journal of The Electrochemical Society, 160(11), A2021. 157. Dai, Y., Li, W., Chen, Z., Zhu, X., Liu, J., Zhao, R., Wright D. S., Noori A., Mousavi M. F., & Zhang, C. (2019). An air-stable electrochromic conjugated microporous polymer as an emerging electrode material for hybrid energy storage systems. Journal of Materials Chemistry A, 7(27), 16397-16405. 158. Yoon, H., Chang, M., & Jang, J. (2007). Formation of 1D poly (3, 4ethylenedioxythiophene) nanomaterials in reverse microemulsions and their application to chemical sensors. Advanced Functional Materials, 17(3), 431-436.

  1. P. Yin, P. Wu, Z. Xiao, D. Li, E. Bitterlich, J. Zhang, P. Cheng, D. V. Vezenov, T. Liu, Y. Wei, Angew.

	ITO	Indium Tin Oxide
	ILs	Ionic Liquids
	IR	infrared	List of Abbreviations
	LUMO	Lowest Unoccupied Molecular Orbital
	3D	three-dimensional
	L	Ligand
	AFM	Atomic Force Microscopy
	M	Metal
	BINOL MOs	1,1'-bi-2-naphthol Molecular Orbitals
	BMIMBF4 MS	1-butyl-3-methylimidazolium tetrafluoroborate mass spectra
	BMIMTf2N	bis[(trifluoromethyl)sulfonyl]imide
	NBu4PF6	tetrabutylammonium hexafluorophosphate
	CP	Conjugated Polymers
	NMP	1-Methyl-2-pyrrolidinone
	CE	Coloration Efficiency
	NMR	nuclear magnetic resonance
	CV	Cyclic Voltammogram
	NIR	near infrared
	DCM	dichloromethane
	NMR	nuclear Magnetic Resonance
	DMF	N,N-dimethylformamid
	DTA	Differential Thermal Analysis
	EQCM	Electrochemistry Quartz Crystal Microbalance
	EC	Ethylene Carbonate
	EMC	Ethyl Methyl Carbonate
	DMC	dimethyl carbonate
	DTAB	dodecyltrimethylammonium bromide
	ECDs	electrochromic devices
	ECSCs	electrochromic supercapacitors
	EDOT	2,3-dihydrothieno-1,4-dioxin
	ESR	Electron Spin Resonance
	EIS	Electrochemical Impedance Spectroscopy
	F-TH	3-(N-trifluoroacetamido)thiophene
	FTO	Fluorine-doped Tin Oxide
	FT-IR	Fourier Transform InfraRed
	HOMO	Highest Occupied Molecular Orbital

Chem. Int. Ed. 2011, 50, 2521-2525. 2. F. Xiao, J. Hao, J. Zhang, C. Lv, P. Yin, L. Wang, Y. Wei, J. Am. Chem. Soc. 2010, 132, 5956-5957. Ethylenedioxythiophene (EDOT)", H. Wang, Y. Shen, P. Ma, A. Bonnefont, Y. Lv*, L. Ruhlmann,*H. Ni, W. Liu, C. Zhang*, ChemElectroChem; 2020, 7, 3038-3043. Auteur correspondant.

Table 1 .

 1 Selected bond lengths (Å) and angles (

o ) are shown in Table

S1

. POT-1 is the first structurally determined POT cage in which the assembly is achieved exclusively by incorporation of polymerizable TA ligand into a TixOy core.

Table 1 .

 1 Details of the structure solution and refinement of POT-1

	Compound	POT-1
	Chemical formula	C54H72S6O24Ti6
	FW	1584.9
	Crystal system	Triclinic
	Space group	P-1
	a (Å)	10.2226(7)
	b (Å)	13.5319(9)
	c (Å)	13.5794(9)
	ɑ( o )	105.493(2)
	β ( o )	99.264(2)
	γ( o )	107.574(2)
	V (Å 3 )	1664.9(2)
	Z	1
	Calculated Density (Mg/m 3 )	1.579
	Absorption coefficient(mm -1 )	0.949
	reflections collected	35237
	independent reflections (Rint)	7666
		( 0.0202)
	R1, wR2 [I>2σ(I)]	0.0331,
		0.0811
	R1, wR2 (all data)	0.0381,
		0.0841

Table 2 .

 2 Details of the structure solution and refinement of POT-2

	Compound	POT-2
	Chemical formula	C34H62O13S2Ti3
	FW	886.60
	Crystal system	Monoclinic
	Space group	P21/n
	a (Å)	12.5531 (8)
	b (Å)	17.3566 (9)
	c (Å)	20.9572 (12)
	β (°)	93.091 (2)
	V (Å 3 )	4559.5 (5)
	Z	4
	Calculated Density (mg/m 3 )	1.283
	Absorption coefficient(mm -1 )	0.66
	reflections collected	20826
	independent reflections (Rint)	4183
		(0.060)
	R1, wR2 [I>2σ(I)]	0.0911,
		0.228
	R1, wR2 (all data)	0.142,
		0.254

Table 3 .

 3 Details of the structure solution and refinement of POT-3.

	Compound	POT-3
	Chemical formula	C34H64N2O13Ti3
	FW	852.55
	Crystal system	Monoclinic
	Space group	P21/n
	a (Å)	12.181 (2)
	b (Å)	25.106 (5)
	c (Å)	14.301 (3)
	β (°)	91.95 (3)
	V (Å 3 )	4370.9 (15)
	Z	4
	Calculated Density (Mg/m 3 )	1.293
	Absorption coefficient(mm -1 )	0.59
	reflections collected	5010
	independent reflections (Rint)	6824
		(0.047)
	R1, wR2 [I>2σ(I)]	0.0453,
		0.142
	R1, wR2 (all data)	0.0626,
		0.156

Table 4 .

 4 Details of the structure solution and refinement of POT-4.

	Compound	POT-4
	Chemical formula	C40H76O16S2Ti4
	FW	1068.72
	Crystal system	Orthorhombic
	Space group	P212121
	a (Å)	12.424(4)
	b (Å)	14.785(2)
	c (Å)	28.947(2)
	V (Å 3 )	5317.3(7)
	Z	4
	Calculated Density (Mg/m 3 )	1.335
	Absorption coefficient(mm -1 )	0.717
	reflections collected	53508
	independent reflections (Rint)	12195 (0.0463)
	R1, wR2 [I>2σ(I)]	0.0413,0.0723
	R1, wR2 (all data)	0.0580,0.0777

2.2.6 Synthesis and Characterisation of [Ti2O(OAc)2(HOAc)2Cl4] (POT-5).

10.0 ml Titanium tetrachloride (91.0 mmol), 20 ml glacial acetic acid (HOAc), 20.0ml dry toluene were mixed together and stirred under nitrogen at 35 °C for 30 minutes, cooling at 1°C per hour to room temperature gave colorless crystals of [Ti2O(OAc)2(HOAc)2Cl4] (POT-5), yield 8.73g (39 % with respect to Ti supplied). IR data (KBr, cm -1 ) for POT-5: 3270s, 2930w, 1636m, 1587m, 1503s, 1489s, 1313w, 1275m, 1147s, 1112s, 1089s, 941w, 825w, 754m, 698m, 626m, 525m.

Table 5

 5 Details of the structure solution and refinement of POT-5.

	Compound	POT-5
	Chemical formula	C8H14Cl4O9Ti2
	FW	491.79
	Crystal system	Orthorhombic
	Space group	Pnma
	Unit cell dimensions
	a (Å)	12.6154(9)
	b (Å)	18.5017(14)
	c (Å)	7.6960(5)
	V (Å 3 )	1796.3(2)
	Z	4
	calc (Mg/m 3 )	1.818
	(Mo-K ) (mm -1 )	1.520
	reflections collected	17798
	independent reflections	1907
	(Rint)	(0.0423)
	R1, wR2 [I>2σ(I)]	0.0435,
		0.1096
	R1, wR2 (all data)	0.0492,
		0.1132

2.2.7 Synthesis and Characterisation of [Ti2(OEt)9InI2] (POT-6).

Titanium(IV) ethoxide (2.0 ml, 8.8 mmol), indium iodide anhydrous (0.495 g, 1 mmol) and absolute ethanol (5 ml) was placed in an autoclave under nitrogen and the mixture heated to 150 o C for 3 days. Colourless crystals of [Ti2(OEt)9InI2] (POT-6) were obtained by cooling to room temperature.

Structure solutions and refinements details of POT-6 are listed in Table

6

, selected bond lengths (Å) and angles ( o ) of POT-6 are shown in Table

S6

. As shown in Figure

29

, sXRD analysis shows that POT-6 contains a Ti2InO5 core, each of Ti(IV) centre is bonded with four bridging ethoxide ligands and two terminal ethoxide ligands to form a six-coordinated octahedral geometry, the In(III) centre is connected with four bridging ethoxide ligands and two terminal iodide ligands and formed a six-coordinated octahedral geometry, too.

Table 6 .

 6 Details of the structure solution and refinement of POT-6.

	Compound	POT-6
	Chemical formula	C18H45I2InO9Ti2
	FW	869.96
	Crystal system	Triclinic
	Space group	P-1
	a (Å)	10.661(5)
	b (Å)	11.329(2)
	c (Å)	15.041(3)
	ɑ ( o )	94.671(6)
	β ( o )	96.478(6)
	γ ( o )	116.08(3)
	V (Å 3 )	1603.6(6)
	Z	2
	Calculated Density (Mg/m 3 )	1.802
	Absorption coefficient(mm -1 )	3.16
	reflections collected	12832
	independent reflections (Rint)	5094 (0.0470)
	R1, wR2 [I>2σ(I)]	0.0980, 0.2462
	R1, wR2 (all data)	0.1103, 0.2509

Table 7 ,

 7

selected bond lengths (Å) and angles ( o ) of POT-7 are shown in Table

S7

.

Table 7

 7 Details of the structure solution and refinement of POT-7

	Compound	POT-7
	Chemical formula	C27H63ClO10Ti3
	FW	726.92
	Crystal system	Tetragonal
	Space group	P43212
	a (Å)	12.6345(10)
	b (Å)	12.6345(10)
	c (Å)	50.131(6)
	V (Å 3 )	8002.5(13)
	Z	8
	Calculated Density (Mg/m 3 )	1.207
	Absorption coefficient(mm -1 )	0.693
	reflections collected	90598
	independent reflections (Rint)	3799 (0.0943)
	R1, wR2 [I>2σ(I)]	0.0669, 0.1907
	R1, wR2 (all data)	0.0786, 0.2060

9 Synthesis and Structure of [Ti3O(CO3 i Pr)(O i Pr)10CoBr] (POT-8).

  Titanium isopropoxide (2 ml, 9.54 mmol), cobalt bromide anhydrous (0.25g, 1.14 mmol) and isopropanol anhydrous (5 ml) was placed in an autoclave under nitrogen

Table 8 .

 8 Details of the structure solution and refinement of POT-8.

	Compound	POT-8
	Chemical formula	C34H77BrCoO14Ti3
	FW	992.50
	Crystal system	Monoclinic
	Space group	P21/c
	a (Å)	11.127(6)
	b (Å)	19.130(2)
	c (Å)	24.610(6)
	β ( o )	107.424(4)
	V (Å 3 )	4998.4(8)
	Z	4
	Calculated Density (Mg/m 3 )	1.319
	Absorption coefficient(mm -1 )	1.639
	reflections collected	79293
		7276
	independent reflections (Rint)	(0.1455)
		0.0562,
	R1, wR2 [I>2σ(I)]	0.1275
	R1, wR2 (all data)	0.0954, 0.1488

Table 9 .

 9 Details of the structure solution and refinement of POT-9.

	Compound	POT-9
	Chemical formula	C42H98CeCl2O16Ti4
	FW	1261.82
	Crystal system	Monoclinic
	Space group	P21/c
	a (Å)	12.822(2)
	b (Å)	15.481(4)
	c (Å)	32.339(3)
	β ( o )	92.822(3)
	V (Å 3 )	6411.2(10)
	Z	4
	Calculated Density (Mg/m 3 )	1.307
	Absorption coefficient(mm -1 )	1.308
	reflections collected	56703
		11236
	independent reflections (Rint)	(0.0758)
	R1, wR2 [I>2σ(I)]	0.0612, 0.1522
	R1, wR2 (all data)	0.0854, 0.1737
	2.2

.11 Synthesis and Structure of [Ti22O28(C2O4)(O i Pr)34Cu] (POT-10).

  , and two O atoms in oxalate anion (C2O4), the oxalate anion bridged two Ti11CuO16 core. So far, reported crystal structures about Cu(II) doped POTs is very rare. What's more, it is notable that the bridging oxalate anion in POT-10 is derived form isopropanol through the in situ oxidation reaction during solvothermal process.

	Titanium isopropoxide (2.0 ml, 9.54 mmol), cuprous iodide anhydrous (0.19g, 1.0
	mmol) and isopropanol anhydrous (5.0 ml) tetrahydrofuran anhydrous (5.0 ml) were
	placed in an autoclave under nitrogen and the mixture heated to 150 o C for 5 days, the
	obtained green solution were futher placed in room temperature, green crystals of
	[Ti22O28(C2O4)(O i Pr)34Cu] (POT-10) were obtained by cooling in four weeks. Yield:
	only trace amount.

As shown in

Figure 33, sXRD analysis shows that POT-10 contains two Ti11CuO16 core, containing eleven Ti(IV) centres and a Cu(II) centre. The Cu(II) centre is fourcoordinated to assume a plane quadrilateral geometry being bonded with two μ3-O oxo-atomsStructure solutions and refinements details of POT-10 are listed in Table 10, selected bond lengths (Å) and angles ( o ) of POT-10 are shown in Table

Table 10 .

 10 Details of the structure solution and refinement of POT-10.

	Compound	POT-10
	Chemical formula	C104H238Cu2O66Ti22
	FW	3725.81
	Crystal system	Triclinic
	Space group	P-1
	a (Å)	14.6523 (9)
	b (Å)	15.1144 (14)
	c (Å)	24.459 (5)
	ɑ ( o )	74.189 (14)
	β ( o )	76.906 (11)
	γ ( o )	66.230 (7)
	V (Å 3 )	4727.6 (12)
	Z	1
	Calculated Density (Mg/m 3 )	1.309
	Absorption coefficient(mm -1 )	1.159
	reflections collected	45351
	independent reflections (Rint)	16615
		(0.0450)
	R1, wR2 [I>2σ(I)]	0.0717,
		0.2049
	R1, wR2 (all data)	0.1092,
		0.2241
	2.2.

12 Synthesis and Structure of [Ti12O16(O i Pr)16][Ti12O15(O i Pr)17] + [(ICo)6Ti15O24(O i Pr)18(I)] - (POT-11).

  Pr)16] [118], only with one of the two μ2-O atoms in this cage being replaced by an isopropoxide group (resulting in a net +1 charge).

	Titanium isopropoxide (2.0 ml, 9.54 mmol), cobalt (II) iodide dihydrate (0.313g, 1.0
	mmol) and isopropanol anhydrous (5 mL) were placed in an autoclave under nitrogen
	at 150 o C for 3 days, the obtained green solution were futher placed in room
	temperature,		blue-green	needle	shaped		crystals	of
	[Ti12O16(O i Pr)16][Ti12O15(O i Pr)17] + [(ICo)6Ti15O24(O i Pr)18(I)] -(POT-11) were selected in
	the mixture of crystals of POTs by cooling in four weeks. Yield 0.063g, 3%.
	As shown in Figure 34, the single-crystal X-ray study of the structure of POT-11
	exists	as	an	ion-separated	arrangement	in	the	solid	state,
	[Ti12O16(O

i Pr)16][Ti12O15(O i Pr)17] + [(ICo)6Ti15O24(O i Pr)18(I)] -. The [Ti12O15(O i Pr)17] + cation of POT-11 is closely related structurally to the previously reported neutral POT

[Ti12O16

(O i

Table 11 .

 11 Details of the structure solution and refinement of POT-11.

	Compound	POT-11
	Chemical formula	C153H357Co6I7O106Ti39
	FW	7002.14
	Crystal system	Trigonal
	Space group	P31m
	a (Å)	24.193(3)
	b (Å)	24.193(3)
	c (Å)	15.185(2)
	ɑ ( o )	90.00
	β ( o )	90.00
	γ ( o )	120.00
	V (Å 3 )	7697.1(17)
	Z	1
	Calculated Density (Mg/m 3 )	1.539
	Absorption coefficient(mm -1 )	2.03
	reflections collected	145905
	independent reflections (Rint)	4912
		(0.1017)
	R1, wR2 [I>2σ(I)]	0.1358,
		0.1671
	R1, wR2 (all data)	0.3327,
		0.3486

Table 12

 12

	Specific surface area and pore parameters of K500, K600, K800, K900, N500, N600, N800, N900.
	sample	SBET(m 2 /g)	Vme(cm 3 /g)	DA (nm)
	K500	46.129	0.194	7.764
	K600	15.252	0.059	7.944
	K800	5.820	0.041	7.732
	K900	5.920	0.050	7.280
	N500	98.914	0.194	4.724
	N600	46.518	0.106	4.611
	N800	66.356	0.156	6.088
	N900	54.036	0.153	6.440
	SBET:specific surface area.
	Vme: mesopore volume calculated by BJH method.

DA: average pore size calculated by BJH method.

Table 14 .

 14 -1 , 837 cm -1 , 778 cm -1 . Selected bond lengths (Å) and angles ( o ) of F-TH

	The crude product was

o C TMS, δ): 8.16 (s, 1H), 7.71 (dd, J=3.2, 1.4Hz, 1H), 7.35 (dd, J = 5.4, 3.2Hz, 1H), 7.11 (dd, J = 5.2, 1.5Hz, 1H). MS (mass m/z): 195 [M + ]. FT-IR: 3284 cm - cm o ) are shown in Table

14

.

Table

13

. Details of the structure solution and refinement of F-TH.

Table 16 .

 16

	Monomer	HOMO/eV	LUMO/eV	Eg/eV
	F-TH	-7.27	-1.29	5.98
	Thiophene	-6.69	-0.70	5.99
	EDOT	-6.12	-0.51	5.61

DFT calculation Data of F-TH, thiophene and EDOT

Table 17 .

 17 Details of the structure solution and refinement of TEPA.

	Compound	TEPA
	Chemical formula	C36H27NO6S3
	FW	665.76
	Crystal system	Monoclinic
	Space group	P21/c
	a (Å)	10.6825 (4)
	b (Å)	15.4602 (9)
	c (Å)	55.789 (3)
	β(°)	93.021 (5)
	V (Å 3 )	9201.0 (8)
	Z	12
	Calculated Density (Mg/m 3 )	1.442
	Absorption coefficient(mm -1 )	0.292
	reflections collected	33718
	independent reflections (Rint)	16191 (0.076)
	R1[I>2σ (I)]	0.088
	wR2 (all data)	0.198

Table 18 .

 18 Selected bond lengths (Å) and angles ( o ) of TEPA.

	Bond	Distance	Bond	Distance
	S1A-C1A	1.667 (13)	S1H-C6H	1.729 (11)
	S1A-C6A	1.720 (11)	S1H-C1H	1.743 (13)
	S1B-C1B	1.702 (12)	S1I-C1I	1.720 (13)
	S1B-C6B	1.765 (11)	S1I-C6I	1.741 (11)
	S1C-C6C	1.738 (11)	N1-C12B	1.419 (12)
	S1C-C1C	1.745 (13)	N1-C12A	1.426 (14)
	S1D-C1D	1.718 (13)	N1-C12C	1.447 (13)
	S1D-C6D	1.746 (11)	N2-C12F	1.398 (12)
	S1E-C1E	1.703 (13)	N2-C12E	1.410 (12)
	S1E-C6E	1.719 (10)	N2-C12D	1.445 (13)
	S1F-C6F	1.665 (11)	N3-C12H	1.416 (14)
	S1F-C1F	1.685 (12)	N3-C12I	1.424 (13)
	S1G-C1G	1.732 (12)	N3-C12G	1.447 (13)
	S1G-C6G	1.742 (11)
	Atoms	Angles	Atoms	Angles

Table 19 .

 19 Hydrogen-bonding geometry (Å, o ) of TEPA.

Table 20 .

 20 Calculated dihedral angle (°) of TEPA over all three independent molecules in unit cell.

	Name	Dihedral angle/°

Table S2 .

 S2 Selected bond lengths (Å) and angles ( o ) of POT-2.

	Bond	Distance	Bond	Distance
	Ti1-O13	1.775 (6)	Ti2-O9	1.987 (5)
	Ti1-O6	1.810 (5)	Ti2-O3	2.044 (5)
	Ti1-O12	1.991 (5)	Ti3-O11	1.788 (5)
	Ti1-O5	1.992 (5)	Ti3-O10	1.796 (5)
	Ti1-O4	2.062 (5)	Ti3-O12	2.018 (5)
	Ti1-O2	2.130 (5)	Ti3-O9	2.019 (5)
	Ti2-O8	1.761 (7)	Ti3-O5	2.022 (4)
	Ti2-O7	1.782 (6)	Ti3-O1	2.146 (5)
	Ti2-O5	1.850 (5)
	O13-Ti1-O6	97.5 (3)	S2-C9-H9	124.5
	O13-Ti1-O12	97.9 (2)	C12-C11-O6	108.6 (11)
	O6-Ti1-O12	103.3 (2)	C12-C11-C13	114.0 (10)
	O13-Ti1-O5	96.8 (2)	O6-C11-C13	110.2 (9)
	Atoms	Angle	Atoms	Angle
	O6-Ti1-O5	165.6 (2)	O8-Ti2-O7	115.9 (3)
	O12-Ti1-O5	76.7 (2)	O8-Ti2-O5	116.4 (3)
	O13-Ti1-O4	91.1 (2)	O7-Ti2-O5	127.4 (3)
	O6-Ti1-O4	91.4 (2)	O8-Ti2-O9	100.7 (3)
	O12-Ti1-O4	161.6 (2)	O7-Ti2-O9	96.8 (3)
	O5-Ti1-O4	86.28 (19)	O5-Ti2-O9	79.1 (2)
	O13-Ti1-O2	174.9 (2)	O8-Ti2-O3	90.4 (2)
	O6-Ti1-O2	83.4 (2)	O7-Ti2-O3	87.0 (2)
	O12-Ti1-O2	86.8 (2)	O5-Ti2-O3	87.2 (2)
	O5-Ti1-O2	82.2 (2)	O9-Ti2-O3	165.2 (2)
	O4-Ti1-O2	83.89 (19)	O10-Ti3-O5	96.3 (2)
	O11-Ti3-O10	95.6 (2)	O12-Ti3-O5	75.43 (19)
	O11-Ti3-O12	104.0 (2)	O9-Ti3-O5	74.5 (2)
	O10-Ti3-O12	96.8 (2)	O11-Ti3-O1	85.5 (2)
	O11-Ti3-O9	103.5 (2)	O10-Ti3-O1	178.6 (2)
	O10-Ti3-O9	95.5 (2)	O12-Ti3-O1	83.8 (2)
	O12-Ti3-O9	148.5 (2)	O9-Ti3-O1	83.4 (2)
	O11-Ti3-O5	168.0 (2)	O5-Ti3-O1	82.53 19)

Table S3 .

 S3 Selected bond lengths (Å) and angles ( o ) of POT-3.

	Bond	Distance	Bond	Distance
	Ti1-O2	1.8017 (19)	Ti2-O6	1.9779 (19)
	Ti1-O7	1.8314 (19)	Ti2-O9	2.0040 (19)
	Ti1-O1	1.9641 (18)	Ti3-O13	1.8133 (19)
	Ti1-O5	2.0233 (18)	Ti3-O3	1.8291 (19)
	Ti1-O6	2.0320 (19)	Ti3-O1	1.9721 (17)
	Ti1-O8	2.1012 (19)	Ti3-O9	2.004 (2)
	Ti2-O11	1.7722 (19)	Ti3-O4	2.0321 (19)
	Ti2-O19	1.782 (2)	Ti3-O12	2.1230 (19)
	Ti2-O1	1.9378 (18)
	Atoms	Angle	Atoms	Angle
	O2-Ti1-O7	95.14 (8)	O11-Ti2-O19	105.39 (10)
	O2-Ti1-O1	170.41 (8)	O11-Ti2-O1	143.70 (9)
	O7-Ti1-O1	94.29 (8)	O19-Ti2-O1	110.86 (9)
	O2-Ti1-O5	94.02 (8)	O11-Ti2-O6	96.65 (9)
	O7-Ti1-O5	93.81 (8)	O19-Ti2-O6	104.02 (10)
	O1-Ti1-O5	87.10 (7)	O1-Ti2-O6	76.80 (7)
	O2-Ti1-O6	102.26 (8)	O11-Ti2-O9	94.33 (9)
	O7-Ti1-O6	95.88 (8)	O19-Ti2-O9	102.11 (10)
	O1-Ti1-O6	74.97 (7)	O1-Ti2-O9	76.42 (7)
	O5-Ti1-O6	160.18 (7)	O6-Ti2-O9	147.73 (8)
	O2-Ti1-O8	84.44 (8)	O1-Ti3-O9	75.66 (7)
	O7-Ti1-O8	178.13 (8)	O13-Ti3-O4	90.04 (8)
	O1-Ti1-O8	86.19 (7)	O3-Ti3-O4	94.45 (8)
	O5-Ti1-O8	84.41 (8)	O1-Ti3-O4	87.84 (7)
	O6-Ti1-O8	85.99 (8)	O9-Ti3-O4	161.87 (8)
	O13-Ti3-O3	95.97 (9)	O13-Ti3-O12	174.47 (8)
	O13-Ti3-O1	97.02 (8)	O3-Ti3-O12	85.20 (8)
	O3-Ti3-O1	166.81 (8)	O1-Ti3-O12	82.09 (8)
	O13-Ti3-O9	99.28 (9)	O9-Ti3-O12	85.82 (8)
	O3-Ti3-O9	99.95 (8)	O4-Ti3-O12	84.47 (8)

, 3159 cm -1 , 3124 cm -1 , 1701 cm -1 , 1595 cm -1 ,1387 cm -1 , 1193 cm -1 , 1152 cm -1 , 964

ACKNOWLEDGEMENTS

I first want to acknowledge all the members of the jury for agreeing to evaluate this thesis: Prof. Laurent RUHLMANN, Université de Strasbourg

activity and can be found in active carbon usually. evacuation and back-filling with argon. Pd(PPh3)4 (82 mg, 0.07 mmol) was added and the reaction mixture was degassed for 10 min with an argon flow. The mixture was then stirred under reflux for 24 h. The solvent was evaporated under vacuum and the residue was partitioned between CH2Cl2 and water, the organic phase was washed with brine and dried over MgSO4 and then the solvent was evaporated under vacuum.

The residue was purified chromatographically (SiO2, PE: CH2Cl2=2:1) giving a yellow solid product of TEPA (0.80 g, yield 86%).

Samples obtained after chromatography were shown to be analytically pure by elemental analysis (calcd for TEPA (C36H27NO6S3): C: H: N: S= 65.0: 4.1: 2.1: 14.4; found: C: H: N: S = 65.0: 4.1: 2.1: 14.4). 1H NMR and FT-IR spectra of the obtained TEPA samples are similar to the reported spectra31 and are shown in Figure 50 and As shown in Figure 84, the electropolymerization process were carried out under conditions similar to those previously reported [182,183], by iterative scans between -1.50 and +1.00 V versus SCE in 0.1 mol L -1 solutions of tetrabutylammonium hexafluorophosphate (NBu4PF6) in 1,2-C2H4Cl2/CH3CN (7/3) containing ZnT2P (0.25 mmol L -1 ) and POT-1 (0.25 mmol L -1 ) under argon atmosphere.

Summary and Scope of Further Work

Summary

The present study has been carried out with the objective to design, synthesize and characterize series of new functional material based on POTs. We tried to study the intrinsic links among micro-structures and electrochemical properties of POTs based material, develop controllable synthesis technologies and obtain POTs based materials with excellent overall performance.

The important results of the present thesis investigation can be summarized as follow:

1. Through solvothermal and solvent diffusion methods, we synthesized twelve different POTs with different formula and structure have been successfully

synthesized and structural determined.

2. Based on obtained POTs, we further prepared a series of novel materials.

C@TiO2 composite materials can be used as electrode materials for Li-ion battery and supercapacitor because of their excellent electricity storage capacity.

PEDOT:Ce@TiO2, Poly-(TEPA-POT-4), have strong hydrophobic surface and exhibit promising electrochromic properties.

General conclusion

The objective of the present thesis was to design and prepare inorganic-organic hybrid materials based on POTs. In this thesis, we designed, synthesized and characterized a series of novel materials based on POTs:TiO2/C composite materials;

CeTixOy/PEDOT composites as well as new copolymer materials Poly-(EDOT-POT-1)

and Poly-(ZnT2P-POT-1). We studied the intrinsic links among micro-structures and electrochemical properties of these novel materials.

In In chapter III, using POT-5 as precursor, as series of C@TiO2 composite materials were obtained through calcined in nitrogen flow or air flow at different temperature.

The C@TiO2 composites calcined in nitrogen named N800. Compare with other C@TiO2 composites calcined in nitrogen (N1000, N900, N800, N700, N600, N500, N400, N300) and air (K300, K400, K500, K600, K700, K800, K900, K1000), N800 exhibits excellent electrochemical performance, which is mainly attributed to the following aspects: the nanoporous structure that can increase the contact area between the electrolyte and the electrode and shorten the transmission distance of lithium ions which ensures rapid charge-discharge performance.

In chapter IV, new synthesis method for hybrid materials based on POT and conducting

List of Publications

Publications in Journals

Presentations in conferences:

Abstract

Functional materials play a vital role and have important scientific significance for researches to meet the worldwide demand for effient and environmentally-friendly technologies and devices for energy conversion and storage. The well-known material, has been widely used in photocatalysis, sensors, solar cells, lithium-ion batteries and other fields. Polyoxotitanates (POTs) containing well-defined ratios of Ti atoms to the dopant metals and/or organic ligands are very interesting since these POTs are potential single source precursors to useful materials such as metal-doped TiO2 with structurally well-defined models for metal-mediated photocatalysis.

In this work, eleven different POTs with different formula and structure have been successfully synthesized and structurally determined. Thereafter, a series of novel materials were prepared based on these original POTs. Composite materials C@TiO2 can be used as electrode materials for Li-ion battery and supercapacitor because of their excellent electricity storage capacity. PEDOT:Ce@TiO2, PTEPA-Ti, Poly-(EDOT-POT-1) have strong hydrophobic surface and exhibit promising electrochromic properties. Especially, the 3D nanoporous film Poly-(EDOT-POT)-1 obtained using Ti6O6(TA)6(iPrO)6) (POT-1, TA = thiophen-3-acetate) is a promising electrode material suitable for fast-ion transport and exhibits improved electrochromic properties and 35% higher capacitance (102.5 F/g) compared to PEDOT (75.8 F/g) at a current density of 1 A/g. The improved performance of the hybrid organic-inorganic material Poly-(EDOT-POT)-1 over the parent organic polymer PEDOT potentially opens up a new avenue of research in this area, with implications to a range of existing functional organic polymers. Poly-(EDOT-POT-1) can be used in electrochromic devices such as electrochromic supercapacitor. Besides, one hybrid polymer with porphyrin and POT-1 subunit has been obtained. The film Poly-(H2T2P-POT-1), exhibits good photocurrent generation behavior, and the control of the thickness of the Poly-(H2T2P-POT-1) film is of great importance to optimize the generation of photocurrent under visible illumination. But the overall conversion efficiency of the sealed cell remains to be studied.

Our work in this thesis will pave the way to fabricate promising electrochromic materials with excellent integrated performance and expand the applications of POTs.

Résumé

Les matériaux fonctionnels jouent un rôle vital et ont une importance scientifique importante pour les recherches visant à répondre à la demande mondiale de technologies et de dispositifs efficaces et respectueux de l'environnement pour la conversion et le stockage de l'énergie. Des matériaux bien connus ont été largement utilisé en photocatalyse, dans le domaine des les capteurs et des cellules solaires, et des batteries lithium-ion. Parmis eux, les polyoxotitanates (POT) contenant des rapports bien définis d'atomes de Ti et de métaux dopants et/ou de ligands organiques sont très intéressants car ils sont des précurseurs potentiels pour former des matériaux dopés tels que le TiO2 avec des applications en photocatalyse pour la remédiation des métaux.

Dans ce travail, douze clusters POT ont été synthétisés avec succès et déterminés structurellement. Par la suite, une série de nouveaux matériaux ont été préparés sur la base de ces POT originaux. Les matériaux composites C@TiO2 peuvent être utilisés comme matériaux d'électrode pour batterie Li Notre travail dans cette thèse ouvrira la voie à la fabrication de matériaux électrochromes prometteurs avec d'excellentes performances intégrées et étendra les applications des POT.