Deuterated Chloroform

COF Covalent Organic Framework COHb Carboxyhemoglobin CHCl3 Chloroform

AcOH

Acetic acid APTES (3-Aminopropyl)triethoxysilane BET

First of all, I would like to sincerely thanks Prof. Véronique Bulach, Dr. Zakaria Halime, Prof.

Marcel Bouvet and Dr. Alexandra Fateeva to have kindly accepted to evaluate and to be part of my PhD defense.

I would like to thank my thesis director, Pr. Claude Gros, as well as my co-director of thesis, Dr. Nicolas Desbois, for instruction and assistance during my PhD thesis and also my life in France and who gave me the material means necessary to carry out this project. And great thanks to Pr. Claude Gros and Dr. Nicolas Desbois who supervise and encourage me practically and emotionally. I would also like to warmly thank Dr. Stéphane Brandès and Dr. Laurie André, aspecially for the long period to characterize the COF materials and analysis of experimental results. I am thinking in particular of Dr. Laurie André for many conversation that apply COF materials to sensor application and development of other new and interesting structure COFs.

I would also like to warmly thank Dr. Valentin Quesneau and Dr. Léo Bucher who gave many helps for corrole chemistry as well as many manipulations I never learned before. They are also my best friend and we have many communications during the time they were in Lab. I would also like to warmly thank our technician Sandrine Pacquelet for her very kind assistance about corrole work. I would also like to thank every member in team P2DA, I am very proud of studying and working here for the whole PhD.

I also would like to thank my parents and wife, they supported me to have further study in France.

Table of content

Chapter 1

General introduction

Chapter 1: General introduction 1.1 Carbon monoxide: a societal issue Carbon monoxide (CO) is a colorless, odorless, tasteless, toxic gas resulting from the incomplete combustion of fuels (Fig. 1). 1 As reference, the Earth's lower atmosphere contains approximately 50-100 ppb of CO. 2 Indoor ambient levels typically range from 0.5 to 5 ppm, and may reach higher values up to 5-15 ppm near gas ovens or near other point of sources, and even higher levels (up to 30 ppm) if the combustion is inefficient. 3,4 The safety guidelines given by the World Health Organization (WHO) for exposure to CO gas are <10 ppm for 8 h and 90 ppm for periods not exceeding 15 min. 2 Carbon monoxide has a great negative impact on the human body (and mammals, pets). When you inhale carbon monoxide at excessive levels, symptoms that commonly occur include headache, dizziness, weakness, vomiting, chest pain, and confusion. 5 Long time exposures, or exposure to a large excess of CO can result in loss of consciousness, arrhythmias, seizures, or even death. The relationship between the concentration(ppm) of CO in air and symptoms are shown in Table 1.

Figure 1. Source of carbon monoxide (CO) emission. 6 Table 1. Relationship between the concentration(ppm) of CO in air and symptoms. The mechanism of carbon monoxide poisoning was revealed by the work of Claude

Bernard and Felix Hoppe-Seyler who independently published the mechanism in 1857. 8 Hemoglobin is a tetramer with 4 oxygen binding sites. However, the affinity for carbon monoxide to the site of the tetramer receptor site is 200-300 times greater than for the oxygen molecule. 9 When inhaled, CO competes with O2 for the heme-binding sites of hemoglobin with much higher affinity. Hemes are most commonly considered as the most important component of hemoglobin. It is a coordination complex which is composed of an iron metal center coordinated to a porphyrin, and with one or two axial ligands. Partial occupation of carbon monoxide binding sites in hemoglobin result in the release of O2 from the remaining heme groups, causing the dissociation curve of O2 and the formation of carboxyhemoglobin (COHb) instead of oxyhemoglobin(O2Hb). 10 The binding reactions of dioxygen and carbon monoxide are shown in Scheme 1.

Scheme 1. Binding reactions of hemoglobin for dioxygen and carbon monoxide.

Thus, the transport and delivery of O2 to the tissues interfere with the binding of CO to hemoglobin, leading to tissue hypoxia and asphyxiation (Fig. 2). 11 Inhalation of CO, at high concentrations, in rodent models causes apoptosis of tissues, particularly in brain regions, associated with CO poisoning and tissue injury. 12 Therefore, it is very important to detect the concentration of CO rapidly and accurately. Nowadays, carbon monoxide detectors have been developed to help reduce the incidence and prevalence of unintentional exposures to CO. 13 Figure 2. Toxic mechanisms of carbon monoxide (CO) with hemoglobin in human body. 14

Carbon monoxide sensors

For the detection of carbon monoxide, various technologies and sensors have been developed such as metal oxide semiconductor, 15 electrochemical sensors, 16 In this part, the different sensors designed for carbon monoxide detection will be detailed.

Metal Oxide Semiconductor (MOS)

Since Brattain and Bardeen discovered that gas absorption changes the conductivity of semiconductor material in 1953, 17 a great amount of research was carried out to produce commercial semiconductor sensors. In 1962, MOS sensors were first proposed by Seiyama et al. 18 and patented by Taguchi. 19 Subsequently, this type of sensors has been investigated worldwide for gas sensing and other applications. Researchers have contributed a lot to the understanding of basic information about general sensing method and mechanisms. In recent years, the priority was oriented towards the development of gas sensor devices optimized for their sensitivity and selectivity towards a specific target gas molecule. MOS gas sensors stand out amongst others because of their simplicity and low cost. 20 MOS are used to detect various gases such as carbon monoxide (CO), 21 carbon dioxide (CO2), 22 hydrogen (H2), 23 ammonia (NH3), 24 hydrogen sulfide (H2S), 25 and nitrogen dioxide (NO2), 26 because of their distinctive characteristics, especially by making use of the gases reactivity with different metals.

Concerning our main objective, the introduction of carbon monoxide sensors based on MOS will be presented hereafter. Up to this day, there have been many metal oxide semiconductors developed to detect carbon monoxide. They are capable of CO detection with appropriate selectivity and high sensitivity. 27 Generally, MOS such as SnO2, 28 ZnO, 29 In2O3, 30 TiO2, 31 CeO2, 32 Fe2O3, 33 WO3, 34 CdO, 35 CuO, 36 composite oxides, 37 and yttria-stabilized zirconia (YSZ) 38 are preferred for CO gas sensing. Among these sensor materials, as things currently stand the best MOS material for the detection of carbon monoxide is SnO2. The mechanism for detecting CO on SnO2 is shown in Fig. 3. The carbon monoxide which is considered as reducing gas react with the chemisorbed oxygen atoms on the SnO2 surface forming into CO2, and injecting immobilized electrons back into SnO2. As a result, it reduces the depletion region and releases the band bending, which leads to a decrease in resistance.

Figure 3. CO-sensing mechanism illustration of the SnO2 composite. 13 Such sensors have been demonstrated to have higher responses to carbon monoxide at lower concentrations than with infrared gas analyzer, 21 and as a result they show great promise for cheaper air quality measurement. But the use of high operating temperatures limits the application of such sensors for domestic use, e.g. in houses, which implies that it is still desirable to minimize the operating temperatures. Furthermore, the selectivity towards CO is not very high, interferences such as acetone, ethanol, hydrogen, and ammonia still show a response to SnO2 sensors, even if the response is low. Also, the stability of the sensors should be considered since they will be used over a long period of time, over which they must keep providing an accurate measurement. This entails a maintenance of the detection abilities, which the sensitivity, selectivity, response time, and recovery time. The ideal gas sensor should have high sensitivity, selectivity, stability, low operating temperature, low response and recovery time, low power consumption, and low manufacturing cost. The performance of gas sensors is highly dependent on the sensor material used to manufacture the sensor. As of now, the disadvantages limiting the development of MOS is mainly the high operating temperature and poor selectivity for similar type of gases (reducing or oxidizing).

Electrochemical sensors

Electrochemical gas sensors, a well-known technology that was developed from the 1950s, was first applied to oxygen monitoring. A glucose biosensor was one of the earliest applications of this technology and it was used to monitor the depletion of oxygen in glucose. Over the following decades, advanced developments were made for the technology, allowing the expansion of the application to a wide variety of target gases for the sensors. Generally, electrochemical gas sensors refer to electrochemical analyzers or detectors, which are designed to monitor or measure the concentration of gases outdoors. An electrochemical gas sensor is generally composed of a working (also named sensing), counter, and reference electrodes, all of those are included in a small device fitted with a membrane allowing the gas to go through.

Electrochemical sensors are based on an electrical signal which is produced by the reaction between gases and an electrode. Most of the electrochemical gas sensors are amperometric sensors. They monitor the target gas by generating a current which possesses a linearly proportional relationship to the gas concentration. The principle of electrochemical sensors is to measure the potential difference between working and reference electrode.

The mechanism for electrochemical sensors monitoring carbon monoxide is based on the measurement of current generated between working and reference electrode, where the oxidation and reduction reaction take place at the same time (see Fig. 4). 39,40 For the sensing process, carbon monoxide are oxidized (Eq. 1) after going through the membrane on the surface of the working electrode giving electrons. 41 On the working electrode, with the oxidation of carbon monoxide, oxygen (O2) is reduced to water on the counter electrode according to the Eq.

2:

Equation 1 CO + H O → CO + 2H + 2e

Equation 2 O + 4H + 4e → 2H O
Reactions on the working and counter electrodes cause the different potential between the two electrodes. Electrons move under the certain voltage to generate current. In certain range, after calibration of current and gas concentration, the dependence of concentrations is linear. 42 During the development of electrochemical gas sensors, there is a limitation: the measurement process can be influenced by interfering substances in the analyzed gas. 43 In the case of positive interference with reducing gases like NH3, SO2 and H2, the readings are higher than the real values, while negative interference happens, the results are underestimated due to oxidizing gases like NO2. 44 It has to be noted also that some electrochemical CO sensors are very sensitive to the presence of hydrogen in the atmosphere.

Figure 4. Mechanism of electrochemical gas sensors for the detection of CO. 45 Except interference gases, accuracy of electrochemical sensors decreases with time going on. There are several factors that contribute to the performance deterioration of sensors such as excessive temperature and humidity. Firstly, temperature is a common factor to reduce the lifespan of sensors. Long time exposure to a temperature higher than 50°C or lower than 0°C, the baseline reading and sensors response can be affected. Secondly, humidity possesses the greatest negative effect on the lifespan of sensors. The appropriate condition for operating electrochemical gas sensors is at a relative humidity around 60 %. A much higher or lower ambient humidity than 60 % change the concentration of the electrolyte inside the sensor, affecting the response time and accuracy. The usual methods to solve those problem is to recalibrate it before using it again, or to replace it, and both are quite costly.

SAW sensors

Surface Acoustic Wave (SAW) sensors consist of a class of microelectromechanical systems that is based on the modulation of surface acoustic waves to detect a physical phenomenon. The structure of a basic SAW sensor is illustrated in Fig. 5. The basic surface acoustic wave device is composed by a piezoelectric substrate with an input impedance transducer (IDT) and an output IDT on the two sides of the substrate part. During the measurement, the surface acoustic waves propagate across the substrate area which is also named delay line. On delay line, the mechanical waves move slower than associated electromagnetic form, making a measurable delay. The operating mechanism of a SAW sensor is converting an electrical input signal into a mechanical wave (direct piezoelectric effect), which can be easily affected by a physical phenomenon. The interfered mechanical wave will be received and translated into an electrical output (indirect piezoelectric effect). Because of the high sensitivity of the mechanical wave, any changes about phase, time delay, amplitude or frequency between input and output signal can be interpreted to determine the concentration of target gas.

Figure 5. Structure of the SAW device used as a signal conditioner. 46 Wohltjen and Dessy introduced SAW technology for chemical sensing applications in 1979. 47 Since 1979, a great attention has been paid to SAW sensors and continuous researches have been carried on it. SAW sensors possess several advantages which make them favored by researchers, such as their small size, low cost, planar structure, manufacturing technology, ultrahigh sensitivity, excellent response time, possibility to be used in wired and wireless mode. 48- 53 In addition, with an appropriate selection of the sensing layer, piezoelectric substrates and IDTs, these sensors show good properties such as ultra-high selectivity, reversibility, stability, linearity and fast response time. [START_REF] Caliendo | Advances in SAW-based gas sensors[END_REF][START_REF] Shiokawa | Surface acoustic wave sensors[END_REF] Furthermore, SAW sensors usually serve as carriers for sensing probe instead of direct probes for targets. 52,[START_REF] Drafts | Acoustic wave technology sensors[END_REF] A ZnO nanorods based wireless SAW sensor has also been reported for the detection of CO, [START_REF] Nikolaev | Preparation and Investigation of ZnO Nanorods Array Based Resistive and SAW CO Gas Sensors[END_REF] but the concentration dependency was not established.

Our team, in collaboration with the Femto-ST institute in Besançon (UBFC) proposed a new type of carbon monoxide sensor relying on a sensitive layer composed of cobalt corrole that shows great affinity toward CO. [START_REF] Vanotti | Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles[END_REF] We have firstly reported experimental data to attest the efficiency of cobalt corrole to trap CO molecules with high selectivity, and secondly, we have established the capability of a Surface Acoustic Wave (SAW) device to probe the mechanical properties of the corroles layer to reveal the adsorption of the target gas (Fig. 6). A cobalt corrole complex, named [5,10,15-tris(2,6-dichlorophenyl)corrole]cobalt(III), was chosen because of its ability to ensure the selective trapping of CO and their ease of synthesis: as already described in previous work. [START_REF] Blondeau-Patissier | Detection and monitoring of carbon monoxide using cobalt corroles film on Love wave devices with delay line configuration[END_REF][START_REF] Barbe | Selective chemisorption of carbon monoxide by organic-inorganic hybrid materials incorporating cobalt(III) corroles as sensing components[END_REF][START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF] Figure 6. SAW sensor based on cobalt corrole for carbon monoxide detection. [START_REF] Vanotti | Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles[END_REF] We have proposed a differential configuration for the sensor to overcome the sensitivity to outer parameters and interfering gases. For this purpose, a reference device based on copper corrole (that does not react with CO) was implemented as part of the sensor. Measurements of carbon monoxide concentration in the 100 -7,000 ppm range in the presence of major interferents such as O2, CO2 and H2O (humidity) were achieved. The impact of these interferents on the sensor's sensitivity was estimated. The results demonstrate a very high selectivity for the studied CO/N2 or CO/O2 binary mixtures at 298 K, whatever the applied pressure. Indeed, the selectivity varies from 35,000 to 21,000 for CO/N2 and from 12,000 to 6,000 for CO/O2 between 0 and 1 atm, respectively. These outcomes point out that the use of cobalt corrole can be considered as an appealing way to build sensible SAW device for CO sensing.

1.3 Corrole and cobalt complex for CO adsorption

Synthesis of Corrole

Porphyrins and corroles are among the most prominent examples in the sub-class of tetrapyrrolic macrocycles. [START_REF] Senge | Classic highlights in porphyrin and porphyrinoid total synthesis and biosynthesis[END_REF] They have a very similar chemical structure, which principally only differs from each other by one carbon atom and the fact that corroles show a higher degree of saturation. This is the main reason why corroles are usually described as analogues of porphyrins lacking one meso-carbon and having one direct pyrrole-pyrrole linkage instead.

The numbering and nomenclature of the corroles are derivated from porphyrins and by analogy we designate the α-and ß-pyrrolic positions for the different sites of the four pyrrole rings, and meso-positions for atoms 5, 10 and 15 (Scheme 2). Consequently, corroles that are substituted at the meso-positions are described by the term of meso-substituted corroles. In order to facilitate assignment, the missing meso-carbon at position 20 is just omitted, so that the inner nitrogen atoms have equal numbers in the porphyrin and corrole systems. The description of corroles bearing different meso-substituents is also reported like porphyrins. They are named by A3, trans-A2B, cis-A2B and ABC corroles (Scheme 3), according to the fact that the corresponding two different substituents are arranged on opposite position or side-by-side.

Likewise, during the development of corrole, the same terminology is used. The transderivatives are more easily accessible by the modern synthetic routes, so this type of corroles are more common. Nevertheless, rational syntheses for the cis-products exist, but are of minor practical importance and less interesting to researchers because they are more difficult and time consuming to prepare.

Scheme 2. Structure and nomenclature of porphyrin and corrole. [START_REF] Dedić | Recent Progress in (Photo-)-Electrochemical Conversion of CO2 With Metal Porphyrinoid-Systems[END_REF] Scheme 3. Structure of A3-, trans-A2B-, cis-A2B-and ABC-corroles. [START_REF] Orłowski | Synthesis of Corroles and Their Heteroanalogs[END_REF] Corroles, possessing three pyrrole-like and one imine-like nitrogen donors, are stronger acids than porphyrins. In addition, because of the four nitrogen atoms working as electron-pair donors, tetrapyrrole ligands in general are interesting partners for metal coordination; there are tri-anions for corroles and di-anions for porphyrins. Then, corroles can stabilize metal ions in a higher oxidation state, having a unique reactivity for low valence metallocorroles. [START_REF] Aviv-Harel | Coordination chemistry of corroles with focus on main group elements[END_REF] Although known since 1964, [START_REF] Johnson | Corroles. Part I. Synthesis[END_REF] a facile 'one-pot' synthesis of corroles was reported separately by two groups. [START_REF] Paolesse | 5,10,15-Triphenylcorrole: a product from a modified Rothemund reaction[END_REF][START_REF] Gross | The First Direct Synthesis of Corroles from Pyrrole[END_REF] After 1999, there was a dramatic increase in the literature about the number of reported corroles. For example, the methodology for obtaining corrole A3 is described below (Scheme 4 where A is the substituent at the 5, 10 and 15-positions, see also Schemes 2 and 3) through a two-step synthesis. The first step involved is the reaction between pyrrole and benzaldehyde. According to a nucleophilic substitution reaction. This step is catalyzed by an acid (usually TFA or HCl). The reaction leads to a mixture of polymers which have various lengths. The second step involves an oxidation reaction related to the ring closure of the polymers (pyrrole-pyrrole coupling). The desired polymer chain for the synthesis of corrole is composed of the condensation of four pyrrole and three aldehyde subunits (called a bilane or tetrapyrrane). [START_REF] Koszarna | Efficient Synthesis of meso-Substituted Corroles in a H2O-MeOH Mixture[END_REF] There may be many methodologies to synthesize corrole in one-pot in the first step, but the second step is almost the same and was detailed by the introduction of an oxidant such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or tetrachloro -1,4benzoquinone (p-chloranil) in an organic solvent such as dichloromethane or chloroform. Due to the production of numerous polymers, the yields for target corrole are usually quite low (5-15 %). [START_REF] Paolesse | 5,10,15-Triphenylcorrole: a product from a modified Rothemund reaction[END_REF][START_REF] Gross | The First Direct Synthesis of Corroles from Pyrrole[END_REF][START_REF] Paolesse | Synthesis and Functionalization of meso-Aryl-Substituted Corroles[END_REF][START_REF] Gross | Solvent-Free Condensation of Pyrrole and Pentafluorobenzaldehyde: A Novel Synthetic Pathway to Corrole and Oligopyrromethenes[END_REF] One of the most efficient methodology was reported by Koszarna and Gryko to synthesize meso-substituted corroles with a water / methanol mixture and catalyzed by HCl. [START_REF] Koszarna | Efficient Synthesis of meso-Substituted Corroles in a H2O-MeOH Mixture[END_REF] The method takes advantage of a difference of solubility between the starting materials and the bilane product. During the reaction, the bilane tends to precipitate because of low solubility in the water / methanol mixture. So, the reaction was effectively stopped at the bilane stage. Then the first step, which aims to obtain the bilane, reduces the formation of porphyrin and other sideproducts. For next step, it's very convenient to isolate the bilane and oxidize it into a corrole macrocycle. According to reported yields, the use of p-chloranil rather than DDQ is better to increase the yields of the corroles' synthesis (between 13 % and 56 %).

Gross and co-workers [START_REF] Gross | The First Direct Synthesis of Corroles from Pyrrole[END_REF] have also developed a solvent-free method with a solid support (florisil, alumina or silica) to synthetize A3 corroles (Scheme 5). [START_REF] Gross | Solvent-Free Condensation of Pyrrole and Pentafluorobenzaldehyde: A Novel Synthetic Pathway to Corrole and Oligopyrromethenes[END_REF] The reaction successfully yielded the desired corroles which contain electron-withdrawing substituents (like fluorine and other halogens) increasing the electrophilic properties of the aldehyde, making -position of the pyrrole more reactive. Yields are generally between 8 % and 11 %.

Scheme 4. Synthetic route to corroles from aldehydes and pyrrole. [START_REF] Zipp | The synthesis and characterization of several corroles : research article[END_REF] Scheme 5. Solvent-free synthesis to A3 corrole. [START_REF] Gross | Solvent-Free Condensation of Pyrrole and Pentafluorobenzaldehyde: A Novel Synthetic Pathway to Corrole and Oligopyrromethenes[END_REF] Koszarna and Gryko have proposed an easier method to obtain corrole in high yields.

Unlike the one-pot synthesis method, their approach starts from the synthesis of a dipyrromethane. Dipyrromethanes are synthesized from pyrrole and aldehyde derivatives catalyzed by a small amount of acid, and the most often used acid is trifluoroacetic acid (TFA).

During the development of corrole chemistry, dipyrromethanes have been considered to be an important intermediate in the synthesis of corroles. [START_REF] Koszarna | Efficient Synthesis of meso-Substituted Corroles in a H2O-MeOH Mixture[END_REF][START_REF] Gryko | A Simple and Versatile One-Pot Synthesis of meso-Substituted trans-A2B-Corroles[END_REF][START_REF] Rao | Rational Syntheses of Porphyrins Bearing up to Four Different Meso Substituents[END_REF] The first step synthesis of dipyrromethanes requires a large excess of pyrrole (typically 40

equivalents of pyrrole for one aldehyde). With a short reaction time (around 15 minutes) and room temperature, the formation of pyrrole polymerization or oligomers were successfully minimized with a wide range of catalyst, resulting in a high yield of dipyrromethane (usually better than 50 %). The large excess of pyrrole is employed to reduce the continued reaction leading to linear and cyclic oligomers or pyrrole-polymers. [START_REF] Laha | A Scalable Synthesis of Meso-Substituted Dipyrromethanes[END_REF] When applied to corrole synthesis, two dipyrromethane units will condensate with an aldehyde derivative under acidic conditions to yield bilane and the followed oxidation of bilane produces a corrole A3 (R = R') or trans A2B

(R  R') (Scheme 6). [START_REF] Koszarna | Efficient Synthesis of meso-Substituted Corroles in a H2O-MeOH Mixture[END_REF][START_REF] Gryko | A Simple and Versatile One-Pot Synthesis of meso-Substituted trans-A2B-Corroles[END_REF]76 Scheme 6. Synthetic route to corroles from dipyrromethane. (i) cat. TFA, 15 min; (ii) CH3OH:H2O = 1:1, cat. HCl (iii) p-chloranil (1 eq). [START_REF] Zipp | The synthesis and characterization of several corroles : research article[END_REF] 1.

Metalation of corrole

Over the first two decades of the new century, various corrole derivatives have been applied

to many fields, and simple synthetic methodologies to prepare metalated corroles have been developed. [77][78][79][80] Among the derivatives of corrole, corrole metal complexes take up an important position. The pioneering utilization of metallocorroles in several disciplines, ranging from medicine to chemical sensors, is a result of both synthetic availability and understanding of their characteristics and physical properties. Nowadays, the list of metals coordinated to a corrole ring is extensive, showing an interesting versatility for a wide application of metallocorroles. 81 The dramatic increase of the metal coordination possibilities makes it possible to compete with the more famous porphyrin and phthalocyanine rings. However, because of the unusual and unique characteristics of this contracted ligand, the production of novel metallocorroles remains a subject of rising interest for researchers. Considering the researches on corrole coordination chemistry, it is possible to give the list of all possible metallocorroles according to the periodic table (Table 2). In the recent years, some more positions of the ''periodic table" of metallocorroles have been filled, welcoming new components, such as Silicon, 82,83 Technetium, 84 Tantalum, 85 Cerium and Lutetium. 86 The development of metal corrole complex chemistry is very close to that of metalloporphyrins. For early time of the coordination chemistry, much of the work on metallocorroles were focused on some transition metals like Mn, Fe, Co, and Cu due to their stable coordination and biological applications. 77,[START_REF] Nmr | MHz, DMSO-d6, 10 L Hydrazine) δ -60.25[END_REF][88][89][90][91][92][93] Novel synthetic strategies, for example for Platinum 94 and Manganese, [START_REF] Nmr | MHz, DMSO-d6, 10 L Hydrazine) δ -60.19[END_REF] have been finely tuned, and a significant number of functionalized corrole complexes have been reported, to satisfy the requirements needed to fit different application fields, ranging from catalysis through antitumor therapeutics to optical sensors. [START_REF] Aviv-Harel | Coordination chemistry of corroles with focus on main group elements[END_REF]90,[96][97][98] Our group has done a lot of research on cobalt corrole complexes and their applications [START_REF] Vanotti | Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles[END_REF][START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF][99][100][101] and this will help us to our research project because it is precisely the cobalt complexes that coordinate the carbon monoxide.

Cobalt corrole

Cobalt complexes of corrole and porphyrin macrocycles were both studied and compared, and it was demonstrated that porphyrins tend to stabilize the (+II) oxidation state of cobalt, while corrole generally stabilize the cobalt metal center at the (+III) oxidation state. 103,104 It was revealed that in both theoretical and experimental studies, the cobalt-corrole complex is a tetra-coordination system which was characterized as an intermediate-spin Co(III) (S=1) center coordinated with a corrole 3-ligand in the square planar molecule. 105,106 In general, there are 4 unpaired electrons for Co 3+ , after the coordination to the tri-anionic corrole, there is unpaired spin density transferred from the paramagnetic Co(III) ion to the π orbitals of the corrole ligand.

The electronic configuration of four coordination system (Co(III)) was proposed as (dxy) 2 (dz 2 ) 2 (dxy,dyz) 2 which is similar to earlier found for isoelectronic S = 1 Fe (II) porphyrins. 105 The system leads to the unoccupied orbitals binding to various axial ligands, such as dimethyl sulfoxide (DMSO), pyridine (Py), triphenylphospine (PPh3), cyano (CN  ), and amine (NH3). 105,[107][108][109][110] The coordination property of Co(III) makes it distinguished from porphyrins. For instance, Co(III) corroles are capable of binding carbon monoxide, [START_REF] Barbe | Selective chemisorption of carbon monoxide by organic-inorganic hybrid materials incorporating cobalt(III) corroles as sensing components[END_REF] while Fe(II) porphyrins have shown little response to CO. 111 It was reported that the different ligands and coordination methods cause different oxidation state of cobalt center in corrole. One part of complexes show hexacoordination and the cobalt was kept at Co(III) state. [START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF] But on the other hand, some cobalt complexes show pentacoordination and the cobalt is kept at the Co(II) oxidation state which is noninnocent. 106,112,113 Considering the present PhD project, cobalt porphyrin derivatives are not applicable to CO sensing purposes. Thus, cobalt corroles become one of the most popular corrole complexes among the corrole metal complex chemistry.

Synthetic methods for preparing corrole complexes are often similar to their porphyrin analogs, by the reactions between the free-base ligand in solution and a simple metal halide or acetate salt, with or without heating. The complexes can be easily isolated by column chromatography. Generally, the cobalt corrole was obtained by heating the free-base corrole with cobalt salt (Co(OAc)2nH2O). Among metal and corrole systems, axial ligands also play an important role which is associated with the electron configuration, stability, and application of the complexes by electronic effects. During the study of ligands on the cobalt center in corrole, triphenylphospine and pyridine have been reported to be the most popular ligands. 106,112,114,115 Furthermore, it is very surprising that the intermediates, five-coordinate Co-corrole with pyridine as ligand, Co[Cor](py), remains poorly characterized except from Co corrole triphenylphosphine complexes which are stable and can be fully characterized. 106,116,117 Scheme 7. The coordination of CO, DMSO and NH3 to cobalt corrole and the reactions between each complexes. [START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF] For cobalt corroles, ligands such as dimethyl sulfoxide (DMSO), pyridine and gas molecules like CO and NH3 can strongly coordinate to the cobalt center, resulting in variations in electron density at the metal ion and oxidation state of metal and ligands (Scheme 7). 106 Furthermore, the moieties (electron-withdrawing or donating groups) anchored to the periphery of the corrole will also influence the magnitude and degree of axial coordination. [START_REF] Koszarna | Efficient Synthesis of meso-Substituted Corroles in a H2O-MeOH Mixture[END_REF] Our lab has reported the synthesis and spectroscopic and e-chem characterizations of various cobalt corroles in great detail including the coordination of cobalt corroles with a single DMSO or two NH3 axial ligands in stable forms. [START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF] Examined by DFT computational study, five coordination with one DMSO ligand and six coordination with two NH3 ligands were proposed. [START_REF] Quesneau | Cobalt Corroles with Bis-Ammonia or Mono-DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties[END_REF] It is difficult to remove the DMSO ligand, and getting the complex into a tetra-coordination requires heating under vacuum. However, it should be noted that ammonia can easily replace the DMSO ligand by forming a hexa-coordination with two NH3 on the cobalt center. Furthermore, the NH3 ligands can be easily removed under vacuum at 80°C and the tetra-coordinated form of cobalt corroles (the active species) allows the detection of CO with high sensitivity and selectivity. 118 Thus, tetra-coordinated cobalt corrole can be more easily obtained by the route shown in Scheme 7, and are of great interest for the application of Surface Acoustic Wave (SAW) sensors to detect trace amounts of carbon monoxide at sub-ppm level in the atmosphere. 119 Very recently, our team in collaboration with Femto-ST institute have described a Surface Acoustic Wave (SAW) device, functionalized with cobalt corrole for the selective detection of CO against N2, O2, CO2 and humidity (which are all known to be major interferents for SAW sensors applied to CO sensing). [START_REF] Vanotti | Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles[END_REF] At a very low relative pressure, we note a very high affinity for CO, which is called chemisorption. (blue line in Fig. 7). At higher pressure the isotherms adsorption of CO showed a chemical-physical adsorption profile. The gas selectivity analysis showed the high selectivity for CO against N2 and O2 and a wide detection range of 100 -7000 ppm. This SAW sensor based on cobalt corrole displays potential to detect CO. However, when applied to a SAW sensor surface, the powder of cobalt corrole can be easily removed because of the weak interaction between the corrole and the sensor surface. So, the application of cobalt corrole to sensors still remains to be improved. Enlightened by the 2D and 3D structure of porous materials, we expect to develop a material composed of cobalt corrole to overcome this weakness of cobalt corrole during the CO detection. In the present work, we were interested in the incorporation of corrole inside such porous structures in order to overcome also the pistacking of corroles, and benefit from the large pores of the materials to enhance the gas adsorption of the final sensing materials and sensors. and N2. [START_REF] Vanotti | Influence of interfering gases on a carbon monoxide differential sensor based on SAW devices functionalized with cobalt and copper corroles[END_REF]

Porous materials

Porous materials display porosity through three or two dimension networks avoiding molecular packing. [120][121][122] For example, COFs are organic amorphous 2D or 3D structures which can be built from corroles and specific platforms. On another hand, metal-organic frameworks (MOFs) are composed of metal ions or clusters connected to each other by organic ligands to form highly crystalline 1D, 2D or 3D structures. The present work will also consider using MOFs as porous support for further corroles insertion.

Porous organic materials are great for the adsorption of greenhouse gases such as methane and carbon dioxide. [123][124][125][126][127][128][129] Porous organic materials can also be productively applied to catalysis, 130,131 proton conduction, 132, 133 gas separation, 134,135 energy storage, 136,137 photoenergy conversion in solar cells, 138 semiconduction, 139,140 photocatalysis and photoluminescence, 141,142 With the development of new synthetic and design strategies, more and more COFs materials with different chemical functions, structures and properties have been reported. 151,152 Due to the diversity together with other advantages such as tunable pore size and functionality, COF materials show great potential in various applications for gas adsorption, storage and separation, sensing, catalysis and biomedicine. [153][154][155] Recently, COFs with various functionality have been widely reported in analytic chemistry. 156,157 For instance, in the field of biomedicine, some COFs have been developed as novel solid carrier or sorbent for the immobilization of enzymes or the capture of target analytes including peptides and other small molecules in complex samples, respectively. 158, 159 Some COFs-based composites have been synthesized as novel stationary phases for separation and detection of important analytes such as isomers and drug molecules. 160,161 Figure 8. Typical porous organic material, namely, COF-5 formed from molecular building blocks. 162 Covalent organic frameworks (COFs), as an emerging new type of porous materials, is two-or three-dimensional (2D or 3D) crystalline porous structures constructed by strong covalent bonds between organic subunits. 145,163 Since the first two 2D COFs materials were tactfully constructed by Yaghi and co-workers in 2005 (Fig. 8) via the dehydration reactions of 1,4-benzenediboronic acid itself (COF-1) or with hexahydroxytriphenylene (COF-5), respectively, COFs chemistry has been developed rapidly and making great progress in the past decade. [164][165][166] In comparison with traditional crystalline porous materials, the COFs consisting of organic building units with different groups by covalent bonding possess many unique advantages including large surface areas, good chemical and thermal stability, tunable porous structure and low density. [167][168][169][170] These advantages together with the highly ordered pore structures make the COFs attract intensive interest of researchers. 130,140,171 To efficiently obtain COFs with high crystallinity and in large scale production, many research groups have explored the synthetic possibility in different ways such as solvothermal, 172, 173 ionothermal, 174, 175 mechanochemical, 176 and microwave synthesis. 177,178 In addition, the different reversible reactions containing the dehydration reaction of boronic acid itself or with catechol, the nitrile cyclotrimerization reaction, and the condensation of aldehyde with amine or hydrazide have been developed to construct novel COFs that mainly include boron-based COFs, triazine-based COFs, imine-based COFs, respectively, and thus expand many types of COFs. 179,180 The synthesis and applications of COFs have evolved considerably over the past 20 years (Fig. 9). Respectively, in 2005 and 2007, extended crystalline 2D COFs (COF-1and COF-5) 164 and 3D COFs (COF-102, COF-103, COF-105 and COF-108) 166 were synthesized using reversible covalent bonds (cyclotrimerization of boronic acids and dehydration reaction of boronic acid with catechol). Since these COFs are composed of strong covalent bonds, they are expected to possess high stability and easy modification of structures. Furthermore, their intrinsic porosity as well as their chemical robustness together make it possible to possess high permanent porosities. nm. With this size, it is big enough to be solved by using Rotation Electron Diffraction (RED). 182 Independently, Wuest and co-workers successfully obtained crystals of nitroso polymer networks suitable for Single Crystal X-ray Diffraction (SXRD) analysis. 183 After that, a woven COF was firstly reported by Yaghi group in 2016 during the development of COFs (Fig. 10). 184 This class of COF materials were made from molecular weaving of distinct threads.

After removing the metal, the crossing networks are completely composed of strong covalent bonds, making these materials essentially COFs. Moreover, 3D-Electron Diffraction Tomography (3D-EDT) could be applied to solve the single crystal structures of these. Finally, in 2018, ultimate control was reached, with the synthesis of 3D COF crystals of up to 60 mm, linked by strong imine bonds. 185 COFs with different topologies and with a wide variety of building blocks. Theoretically, according to the dimension and geometry of the building blocks, the topologies of the target COFs can be pre-determined. Compared to other porous materials, especially pure organic polymers, this property of COFs which allows to pre-design the skeleton of the structures is unique, and also helps to analyze and understand the crystal structure of COFs. This exceptional ability allows the construction of complex geometries with highly ordered structures, rather than primary-ordered structures. [186][187][188] The diagram of topology shown in Fig. 11 provides a systematic solution to obtain porous polymers through the combination of building blocks to form organic frameworks yielding crystalline networks with alternately placed linkers and knots. 189,190 Depending on the geometries and dimensions of the knots and linkers, 186 the shape of the formed polygonal skeletons show great variety. Generally, COFs are classified into two categories: 2D and 3D. Based on their geometries, all monomers used to design 2D COFs are categorized into C1, C2, C3, C4 and C6 symmetries (Fig. 11). On the other hand, 3D COFs are pre-designed with a Td symmetric moiety or an orthogonal unit as the knot which will be combined with the different linkers. In the following part, an overview of most often reported principles for the design of COFs is presented. For 2D COFs (Fig. 11a), the hexagonal topology is the most often reported and usually consists of (C2 + C2 + C2) or (C3 + C2) or (C3 + C3) but with different pore sizes and π-orderings.

For example, reported by Côté and co-workers, the condensation of a C3 symmetry with a C2 linear linker (C3 + C2) yields an hexagonal COF. 164,192 A self-condensation of the C2-symmetric unit could also provide a hexagonal COF, 140,164,193 , as well as the reaction of two building units having a trigonal planar C3 + C3 geometry. [194][195][196][197][198] Besides the hexagonal topology, tetragonal topology is also very popular among 2D COFs. With the combination of (C4 + C2) the produced sheets, of planar material, feature tetragonal pores. 199,200 It is worthy to note that tetragonal COFs are usually composed of porphyrin derivatives because of their unique C4-symmetry.

Among C2 symmetries, there are platforms also featuring four coupling functions such as 4,4',4'',4'''-(Pyrene-1,3,6,8-tetrayl)-tetraaniline or 4,4',4'',4'''-(Ethene-1,1,2,2-tetrayl)tetraaniline (Scheme 8) which is used to produce either a single-pore rhombic structure or a dual-pore kagome structure. 187,201,202 The kagome network consists of two types of pores in which each hexagonal pore is surrounded by six trigonal pores, while there is only one type of pore in the rhombic network. And finally, the (C6 + C2) combination produces a trigonal topology. 203 The trigonal, tetragonal, rhombic and hexagonal topologies are the major forms of 2D COFs. Besides those common topologies, the combination of three different monomers with appropriate symmetries have been developed to produce complex 2D COFs bearing multi pores. 204 However, all of the 2D COFs have in common that they generate extended onedimensional (1D) channels through stacked layers. 205,206 Scheme 8. Structures of C2 symmetries for single-pore rhombic or dual-pore kagome structures. 187,202 In contrast with 2D COFs that require planar building blocks, 3D COFs usually contain at least one knot having a Td or orthogonal geometry to support the extension of covalently linked 3D network. For this, there are different possible combinations of Td, or orthogonal, knot with C1, C2, C3, C4 or Td symmetry to form skeletons and pores (Fig. 11b). 207,208 3D COFs can be categorized among different types of topologies, including dia, pts, ctn, bor, lon, and ffc. 191 Up to now, the largest number of 3D COFs have been developed using a (C2 + Td) geometry system, which yields dia topology networks. 145,209,210 By changing the C2-symmetric monomers, a great deal of new 3D COF based on dia topology can be obtained easily.

Furthermore, the different topology networks can be achieved by replacing the C2-symmetric monomers with monomers presenting a different symmetry. For example, the ctn or bor network can be obtained by the (C3 + Td) combination with large surface areas without interpenetration inside the skeleton. 166,211,212 The lon network can be designed through (Td + Td). 166 On the basis of the (C2 + Td) and (C4 + Td) combinations, the pts nets are obtained in a two-fold interpenetrated form. 213,214 For pts net, the engaged C2-or C4-symmetric units are required to have four reactive functions. The (C3 + C2) topology has been used to prepare rare examples of 3D COF having an ffc net. 208,215 Interestingly, in 2016, a woven 3D-COF (Fig. 10), named COF-505, has been constructed using helical organic threads by the simple imine polycondensation of benzidine (BZ) with copper(I)-bisphenanthroline tetrafluoroborate (Cu(PDB)2(BF4)) which possess four aldehyde groups. 184 The topology diagram in Fig. 11 can be considered as the general basis for the construction and design of COFs. The high design ability of COFs is a unique feature which is difficult to obtain in other porous materials. Thus, COFs are taken into consideration as attractive materials that have diverse structures and functions.

Bond formation for COFs synthesis

In the previous part, a topology diagram was discussed as the key point to design the COFs structures. Now, we need to note that the synthesis of COF material is mainly influenced by diverse reversible reactions. The synthesis of polymeric materials has generally been dominated by kinetically controlled reactions, which is irreversible reactions, leading to a difficulty to obtain crystalline organic polymers. 216 In order to prevent the formation of disordered kinetic products that are amorphous, it's very important to involve reversible reactions in the synthesis of COF. The reversibility of the bond-forming reaction, together with the help of dynamic covalent chemistry (DCC), 217 in covalent bond formation, allows error correction during the crystallization of COFs which helps the material to attain a higher crystallinity (Fig. 12). In contrast to kinetically controlled reactions, DCC requires a high temperature to give high activation energies to enable the thermal reversibility. Furthermore, a specific agent (water) was used to maintain the reversibility during the covalent bond formation. 164 Therefore, during the COF synthesis, the conditions of reaction are usually dominated by high temperature and catalytic amount of water. Generally, COF is one of the porous organic polymers (POPs), but according to crystallinity, POPs are divided into crystalline and amorphous. The crystalline one is called COF, the other is amorphous POP. The POPs mentioned in the rest part refers to amorphous one. Based on the paradigm of reversible covalent bond formation governing the synthesis of crystalline covalent organic materials, many new reactions have been developed since the discovery of first COFs. In 2005, Yaghi and co-workers reported the first two members, COF-1 and COF-5, which can be synthesized using a simple "one-pot" procedure under mild reaction conditions in high yields. 164 These two materials showed rigid structures, high thermal stabilities, low densities, high surface areas and permanent porosity, tending to be excellent porous materials. Since then, diverse boron-containing COFs have been constructed with boronic esters or boron anhydrides (boroxine). According to the condensation strategy, the resulted boronic COFs can be categorized into two types: self-condensation of boronic acids to boroxine rings and the cocondensation of boronic acids and catechols to boronic esters. The first COF (COF-1) was prepared though self-condensation of a single building block, yielding boroxine-linked COF (Fig. 14a). The boroxine network COF-1 was formed by self-condensation of 1,4-benzene diboronic acid (BDBA). The COF-1 was expanded with porous 2D graphitic layers, featuring highly crystallinity and high surface area of 711 m 2 g -1 . During researches of 2D COFs, the eclipsed stacking motive tends to be one of the necessary characterization of structures.

Surprisingly, with solvent guest molecules, the COF-1 showed an AB stacking mode. Upon removal of solvent guest molecules, these layers shift toward an AA stacking mode. 164 For the boronate esters COF-5, the network was constructed through co-condensation of boronic acids and catechol derivatives, leading to five-membered ring. By the co-condensation of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and BDBA, the hexagonal framework COF-5 eclipsed an AA stacking with hexagonal 1D channels of 2.7 nm in diameter, featuring highly crystallinity and high surface area of 1590 m 2 g -1 . Recently, two other types of boron-containing COFs have been reported with borosilicate cage and spiroborate linkages. COF-202, with a borosilicate cage linkage, was synthesized via co-condensation of tert-butylsilane triol(t-BuSi(OH)3) and tetra(4dihydroxyborylphenyl)methane (Fig. 15). 218 Unlike the condensation of boronic acid and diol (Fig. 14b), in this case, the two hydroxyl groups of one -B(OH)2 react individually with different triols. COF-202 has a high thermal stability (up to 450°C) and great resistance to common organic solvents. Moreover, samples of COF-202 maintain both their porosity and their crystallinity after exposure to air for 24 h. 218 Finally, Brunauer-Emmet-Teller (BET) models yielded high surface area values of 2690 m 2 g -1 .

Figure 15. Synthesis of molecular borosilicate cage (C) and COF-202 (F). 218 Spiroborates, ionic derivatives of boronic acid, have been reported for high resistance toward hydrolysis and high stability in water, methanol, and under basic conditions while boroxine and boronic esters are easy to decompose when encountered with water even in air. 224 With their ionic properties, spiroborates materials tend to function as ion conductive materials for battery application. Up to date, there are rare examples for spiroborates linkage COFs. In 2016, Zhang and his group reported the design and synthesis of porous spiroborate-linked ionic COFs (ICOF-1 and ICOF-2) that exhibit high surface areas, good thermal stability, great resistance to hydrolysis, and high room-temperature ion conductivity. 224 The ICOFs were obtained through the transesterification between borate and polyols by the addition of base catalyst (Fig. 16). The other example of spiroborate COF was reported in 2021. 231 Wang and co-workers designed and synthesized porous cubic 3D COFs (Fig. 17), showing cubic pores, high crystallinity, high surface areas (up to 1726 m 2 g -1 ) and permanent porosity. They also showed good stability in common organic solvents and aqueous solutions except acidic solution. The synthesis is shown in Fig. 18. During the formation of this structure, the diamond topology was expected. However, the big pores are occupied by the long rod-like linkages, thus resulting in 5-fold interpenetrated structures. 209,233 The FT-IR spectrum of COF-300 showed the C=N stretching modes at 1620 cm -1 which is characteristic for imines. 234 Thermal gravimetric analysis shows good thermal stability of COF-300 up to 490 °C. Also, the material is insoluble in water and common organic solvents such showing that the COF-300 is a typically microporous organic material.

Application of COFs

COFs combine a number of physical and chemical properties, they are unique among various porous organic materials. 248 For these reasons, COFs tend to be promising subjects for the development of various fields. After the first reported COF, there are already a large number of new COF structures available in the literature, concerning the most varied applications, such as gas storage and separation, 249, 250 heterogeneous catalysis, 251, 252 chemical sensing, 253,254 controlled drug release, 255, 256 ionic-exchange processes, 257, 258 photoconductivity, 259, 260 energy storage. 261,262 In the following section, some of those applications will be highlighted.

1) Gas adsorption

Due to the high porosity and low density for these COFs materials, gas adsorption tends to be one of the most potential application of these materials. 248 In the past decade, many researches have been carried out to implement COFs as gas storage materials for relevant compounds such as hydrogen (H2), 263 carbon dioxide (CO2), 264 methane (CH4), 265 and ammonia (NH3). 266 Many research works are interesting in the storage of hydrogen because it is a clean source of energy. However, due to the very low density, the storage of hydrogen requires a very high pressure (350 -700 bar) as gas state or very low temperature to keep it as a liquid.

Furthermore, the high instability and reactivity make it more difficult to have large scale distribution of hydrogen. Recent years, among all the porous materials for hydrogen storage, COFs rise as one of the most promising class of materials for H2 storage. 267 For example, the COF-102 (Fig. 23), a 3D framework synthesized by the self-condensation of tetra(4dihydroxyborylphenyl)methane, exhibits a maximum adsorption capacity for H2 of 77 mg g -1 at 35 bar and 77 K. This result shows a competition against the best MOFs and other porous materials for H2 capacity at similar high pressure and almost meeting the current benchmarks established for implementing and construction of fuel cells of H2 viable. 263,268 Figure 23. Synthesis of COF-102 and the corresponding expanded ctn networks. 166 2) Heterogeneous catalysis

Over several decades, heterogeneous catalysis has been considered as the use of functional porous materials with large surface areas. Among these porous materials, amorphous porous organic polymers and crystalline MOFs have been suggested as candidates for efficient heterogeneous catalysts in fine chemical synthesis. [269][270][271][272] As one of the most important members of porous materials, functional COF materials are expected to possess high and efficient potentials as new catalysts. As the cases of other porous solids, COF materials for catalytic application must possess high stability to thermal treatments, water, and most of the organic solvents. 273 Furthermore, for the ideal catalytic performance, it is necessary to have easy accessibility to the catalytic sites and the efficient mass transport inside the porous catalyst. In 2011, the first application of COF for highly efficient catalysis was performed by Wang et al. 130 In order to obtain the palladium loaded COF, the imine-linked COF(COF-LZU1) was firstly synthesized from simple building blocks p-phenylenediamine and 1,3,5benzenetricarboxaldehyde (Fig. 19). The 2D eclipsed layered-sheet structure of COF-LZU1 makes the distance of nitrogen atoms to 3.7 Å in the adjacent layers, which is suitable for the strong coordination of metal ions. Then, the COF was treated with Pd(OAc)2 to form Pd(II)coordinated COF-LZU1 (Fig. 19). The Pd/COF-LZU1 was applied to catalyze the Suzuki-Miyaura coupling reaction. The catalytic performance was demonstrated with the wide range of reactants showing the excellent yields (96%-98%) of products, along with high stability and recyclability as catalyst.

It should be noted that compared to Pd(II)-containing MOF, 274 Pd/COF-LZU1 requires lower palladium loaded rate and thus shows faster reaction speed and higher reaction yield.

These advantages should be assigned to the suitable distance between the 2D layered-sheet.

Nitrogen atoms in adjacent layers can easily incorporate palladium, forming a robust scaffold.

Moreover, the regular channels with a diameter of 1.8 nm ensure efficient access to these active sites as well as rapid diffusion of the bulky products. Up to date, a great breakthrough has been made to explore functional COFs materials as catalysts with broad catalytic sites, various structures even from milligram to gram-scaled synthesis. [275][276][277][278] 3) Photoelectric application Pyrene-functionalized COFs were developed by Jiang and co-workers for photoelectric applications. 139,140 PPy-COF and TP-COF possessing 2D structures with high BET surface areas were obtained by the self-condensation and co-condensation of pyrene-2,7-diboronic acid and2, 3,6,7,10,11-hexahydroxytriphenylene (Fig. 24). Both of them show the capacity of harvesting photons from ultraviolet to visible regions and electrical conductivity. The unique properties of these optoelectronic COFs represent an important step toward the applications of functional COFs in optoelectronics and photovoltaics.

Porous organic polymers

Porous organic polymers (POPs) are a class of porous network polymers formed through covalent linkages between organic components. According to the crystallinity, POPs can be generally divided into crystalline materials and amorphous ones (Fig. 27). Amorphous porous organic polymers have been explored into polymers of intrinsic micropores (PIMs), 282,283 conjugated microporous polymers (CMPs), 284,285 porous aromatic frameworks (PAFs), So far to our knowledge, there are only two examples of POPs based on corroles. The first example from our lab was reported in 2019 (Fig. 28). 302 POPs were prepared starting from tetrahedral-shaped building blocks and corrole macrocyclic linkers either as free bases or cobalt complexes. Fig. 28 shows two different synthetic strategies incorporating cobalt corroles into the porous matrix based on Sonogashira cross-coupling reaction between tetra-alkenyl building blocks and diodo-corrole linkers. The resulted POPs with cobalt corrole showed high permanent porosities and outstanding CO sorption properties with a high selectivity over N2, O2 and CO2.

Another example of corrole-based POP was published recently by Zhao et al. in 2022 (Fig. 29). 303 They have reported porous organic polymers constructed from either Mn or Fe-corrole complexes through Suzuki cross-coupling reaction. The ideal computer-modeled structure is shown in Fig. 29b. The resulted polymers are 2D porous organic polymers, as expected.

However, like most amorphous POPs, the PXRD patterns reveal that these CorPOPs are amorphous rather than crystalline. The CorPOP-1(Mn) displays a superior heterogeneous catalytic activity toward solvent-free cycloaddition of carbon dioxide (CO2) with high recyclability and stability. These two recent publications on corrole-based porous organic polymers highlight the potential of corrole to construct porous materials for different applications. We were thus inspired by this work to obtain new POPs based on cobalt corrole for CO sorption. properties such as high crystallinity, large surface area (ranging from 1000 to 10,000 m 2 /g), high porosity, designable structures compared to traditional porous materials such as zeolites and activated carbons. [304][305][306] The MOFs family has been explored in the past decades since

Yaghi 307 firstly pioneered MOFs in the late 1990s and is still growing rapidly, with thousands of papers published each year. 308 After that, MOFs were distinguished with permanent porosity and high surface areas, due to the strong bonds between metal ions and charged organic ligands. 309 With diversified structures, the pore sizes of MOFs are highly tunable (up to 9.8 nm).

With a large variety of metal nodes and theoretically unlimited number of organic likers, it is easy to tune the compositions and structures of MOFs to achieve targeted functionality in a precise manner. Due to the well-organized structures, huge surface areas, pore volumes, pore size distributions and easily-decorated channels, MOFs have become promising candidates in many applications, including gas storage and separation, 310, 311 luminescence, 312, 313 thin films, 314, 315 proton conduction, 316, 317 catalysis, 318 drug delivery, 319,320 and energy storage and conversion. 321,322 Here we only give a brief introduction to the design of MOFs. Different from COFs or other porous organic materials constructed by organic bonds, MOFs are formed by coordination between metals or metal ions (clusters, multinuclear complexes) and organic multidentate ligands (linkers, see Fig. 30). Basically, the coordination network of MOFs extends through repeating coordination entities in 1, 2, or 3 dimensions. However, during the MOF formation, the fact is that thousands of clusters and linkers can lead to a mixture of molecular 0D complexes, 1D chains, 2D sheets, and 3D frameworks. In order to avoid chaos and obtain the targeted frameworks, mathematical graph theory was applied to design, present and classify the frameworks. Until now, the wide range of these inorganic and organic building blocks offers a great number of MOF topology, enormous flexibility in pore size, shape, and structure, and myriad opportunities for functionalization and grafting which are suitable for a variety of applications. constructed directly from iron-corrole complex and Zr6 cluster displayed efficiently catalyze hetero-Diels-Alder (HDA) reactions between unactivated aldehydes and a simple diene. We will thus be able to take inspiration from these results to build a new MOF based on cobaltcorrole complex for CO sorption. The early detection of carbon monoxide at low levels is a technological challenge with public and industrial health issues. The electrochemical and semiconductor technologies currently developed make it possible to detect carbon monoxide at concentrations of the order of ten ppm, these thresholds make it possible to avoid fatal intoxication but do not correspond to the criteria of purity of industrial gases or chronic poisoning with low levels of carbon monoxide. In addition, these sensors are not very selective and sensitive to other reducing gases.

Infrared detectors allow much lower sensitivity and better selectivity, but their price and size reduce this technology to a niche market. Emerging technologies, especially colorimetric detection, allow low detection thresholds to be reached, but detection reactions are generally irreversible and often not very selective.

During our thesis work, we were therefore interested in SAW sensors. In order to obtain new carbon monoxide detectors, it is necessary to focus first on the development of new sensitive films for these sensors. We therefore decided to focus our work on the development of new porous materials containing cobalt corroles in order to study the efficiency of the metal center on the adsorption of carbon monoxide. We also plan to study the stability and reversibility of these porous materials based on cobalt corroles and to study their gas sorption properties. The ultimate objective of our work is to deposit these new compounds on SAW sensors in order to test them in real conditions (presence of humidity and oxygen) for further detection of CO. The first part of this thesis will deal with the synthesis of various precursors (free-base corroles, porphyrin and platforms) making it possible to obtain new porous materials.

Thus, the second part will deal with the synthesis and characterization of COFs. The properties of COFs for the detection of carbon monoxide will also be described in this part.

76. Lee, C.-H.; S. Lindsey, J., One-flask synthesis of meso-substituted dipyrromethanes and their application in the synthesis of trans-substituted porphyrin building blocks. The first objective of this work was to synthesize porous materials based on free-base corroles or cobalt corrole complexes. This part will be devoted to the synthesis and spectroscopic characterization of porous materials as well as their precursors including platforms and linkers. Here, the porous materials refer to Covalent Organic Frameworks (COFs),

Metal Organic Frameworks (MOFs) and Porous Organic Polymers (POPs). For each type of porous materials (as well as for the precursors), we have designed different synthetic approaches.

Precursors for COFs

Accordingly, covalent organic frameworks are constructed from organic units which are often named as linker and knot. 1,2 Through the combination of linkers and knots, it is convenient to obtain various COFs with different topologies. In this part, linkers refer to corroles and knots are called platforms. Furthermore, the choice for linkages is another key point to synthesize COFs. Among diverse reversible reactions, Schiff base reactions tend to be the first pick to synthesize COFs due to their high stability, smooth synthetic condition and wide range of aldehyde-and amino-functions available. 3,4 All the COFs are based on the Schiff base reaction, thus, the linkers and platforms contain aldehyde-or amino-groups respectively.

Synthesis of corroles

The corroles used for imine COFs work as linkers which bear the same functions (aldehyde or amine) on the 5,15-meso-positions. The general structure of all corroles is trans-A2B-corrole (Scheme 1). Thus, through the combination of trans-A2B-corrole with diverse platforms, new originals COFs could be obtained. At the 10-meso-position of corrole, -CF3 functions were introduced for the first tests. On one hand, as strong electron withdrawing group, -CF3 helps to increase the corrole stability. On the other hand, we have found good CO binding ability using cobalt A3-corrole complexes bearing CF3-functional groups.

Scheme 1. General structure for targeted trans-A2B-corroles.

For the synthesis of trans-A2B-corrole, the classic strategy starting from aromatic aldehydes and dipyrromethanes was mainly applied (Scheme 2). According to the protocol 5,6 from Gryko et al., slight modifications of the synthetic conditions were made.

Scheme 2. Synthesis of trans-A2B-corroles from dipyrromethane and aromatic aldehydes using different conditions (a) or (b). 7 2.1.1.1 Synthesis of aldehyde-functionalized corroles (refer to bis-CHO-corrole)

It is very difficult (or impossible) to directly apply 5-(4-formylphenyl)dipyrromethane to synthesize bis-CHO-corroles (Scheme 3). The aldehyde introduced at the meso-position of the dipyrromethane can react also with another dipyrromethane to form polymers. However, there

are few examples of meso-aldehyde substituted corroles in the literature. [8][9][10] To temporary protect the aldehyde functions, we have designed and tried several synthetic routes.

Scheme 3. Impossible way to synthesize bis-CHO-corrole from 5-(4-formylphenyl)dipyrromethane.

1) Synthesis of acetaldipyrromethane

We firstly tried to design and synthesize a dipyrromethane with a protected aldehyde function (Scheme 4). Using p-TsOH as a catalyst, the aldehyde was protected by the acetal reaction 11 which is reversible and can lead the aldehyde back under acid condition. A formylation reaction 12 follows to give aldehyde 2 which can further react with pyrrole to afford dipyrromethane 5. According to the literature 13 , the synthesis of targeted dipyrromethane 5 was carried with trifluoroacetic acid as catalyst. With a slight change of the amount of pyrrole ( 75times of aldehyde), we got a 71% yield higher than the reported 48% one. We also tried MgBr2 to obtain targeted dipyrromethane according to literature. 14 Usually, with MgBr2 as catalyst for meso-substituted dipyrromethane synthesis, the yield and purity of products tend to be very high. However, in our case, it was quite surprising that almost no targeted dipyrromethane was observed under MgBr2 catalysis. Instead, by 1 H NMR (Fig. 1), we have seen on the NMR spectrum that the main resulted compound was 1,4-bis(dipyrromethane-5-yl)benzene 15 (Scheme 5). In the 1 H NMR spectrum with DMSO-d6, it was found two single peaks at 1.17 and 0.74 ppm which represent two CH3 moieties from the acetal group. The single peak at 10.50 ppm can be assigned to H from pyrroles. The characteristic peak at 5.29 ppm is attributed to the two methane structure (CH). The single peak at 7.07 ppm represented the H from phenyl. And the peaks at 6.57 ppm, 5.89 ppm, 5.67 ppm should be assigned to the -H

and -H of pyrroles. By integration, the ratio for the bis-dipyrromethane and dipyrromethane 5 was 4:1. This could be assigned to MgBr2 which is a strong Lewis acid that could facilitate the hydrolysis of the acetal function. 2) Synthesis of bis-CHO-corrole Generally, synthesis of corroles starting from dipyrromethane and aldehyde are mainly based on two experimental conditions: (1) TFA/ DCM; or (2) H2O/MeOH/HCl. Here, we tried both of them to synthesize bis-acetalcorroles (Scheme 6). When using TFA/DCM conditions, the reaction resulted in almost no product. We assumed that during hours of reaction, the acetal was deprotected to aldehyde and further polymerization occurred. When carrying out the reaction in H2O/MeOH/HCl, the targeted bis-acetalcorrole can be observed. Through the analysis of the mass spectrum after purification, we found the presence of some side products containing either one or two aldehyde functions which were deprotected from the acetal during the corrole synthesis. In the mass spectrum, the targeted corrole was found at m/z = 823.342 while peaks at m/z = 737.264 and 651.170 were observed corresponding to one aldehyde and two aldehyde side products (Fig. 2), respectively. Scheme 6. Synthetic routes of bis-CHO-corrole. Yield : 5.6% (from dipyrromethane) Furthermore, the polarities of the compounds are very close and it's difficult to separate them from the mixture. Thus, we directly used mixture corroles 13 for the next step to produce bis-CHO-corrole 14. In addition, the yields for these two corroles were around 8-10%. Thus, we have used the mixture directly for the next step. The hydrolysis of the acetal (partially deprotected corrole) was carried out in a mixture of TFA, THF and H2O at 70°C. The general yield from dipyrromethane (2 steps) was 5.6%. The low yield of the bis-aldehyde corrole was an inconvenient and also uneconomic to further consider a larger scale of corroles for COF synthesis. The synthesis of COFs from bis-CHO-corrole 14 will be detailed in Chapter 3.

Synthesis of amino-functionalized corrole (refer to bis-NH2-corrole)

We have also designed and synthesized corroles bearing amino functions on the 5,15-mesopositions. To the best of our knowledge, it's impossible to directly synthesize corrole from precursors with amino functions, as the latter are easily oxidized. The synthesis of amino containing corroles has been reported in the literatures during the past decades. [16][17][18] Generally, the amino derivatives are hydrogenated from nitro corroles mainly with two different methods:

(1) Pd/C/ H2; (2) SnCl2/HCl. Inspired by the literature, we choose to conduct hydrogenation of corrole under hydrogen atmosphere with palladium on carbon as catalyst well known to lead to high yields and to process through clean reaction. The reaction condition was modified slightly according to the synthesis of 5,10,15-tris(4-aminophenyl)-corrole reported by Gros et al. 17 1) Synthesis of nitrodipyrromethane Similarly, the first step is the synthesis of dipyrromethane bearing a nitro functional group at the meso-position (Scheme 7). To obtain a high yield and pure dipyrromethane, MgBr2 was chosen as the catalyst. 14 In an one pot reaction, the quantity of isolated product can reach to 12 g, which make sure that we can easily have enough dipyrromethane for the corrole synthesis. Scheme 7. Synthesis of 5-(4-nitrophenyl)dipyrromethane.

2) Synthesis of bis-amino-corrole

Based on the targeted trans-A2B-corrole structure, the bis-nitro corrole was synthesized from 5-(4-nitrophenyl)dipyrromethane and 4-(trifluoromethyl)benzaldehyde using H2O/MeOH/HCl conditions (Scheme 8). In order to compare the COF synthesis from aldehyde and amino corrole, we kept the same -CF3 moiety at the 10-meso-position of the corrole. As expected, this step gave a good yield of 38%. In addition, the purification of the bis-nitro corrole is easy via a fast column chromatography followed by recrystallization in DCM and heptane.

For the hydrogenation of the nitro functions, the Pd/C catalyst was activated by heating under vacuum to avoid side products. After loading all the solvent and reagents, the reactor was purged with hydrogen. The process of the reaction was monitored by mass spectrometry until the two nitro functions were reduced to amino groups. The resulted compound was purified by flash chromatography (1g per batch with solid deposit) with DCM/TEA (v:v =100:1) as eluent.

The targeted bis-amino corrole was obtained with 85% yield and was very pure. During the whole synthetic route, we have used 4-(trifluoromethyl)benzaldehyde to functionalize the meso-positions of the corrole macrocycle. With the same moiety at the meso-position, it is convenient to compare the properties of synthesized COFs.

Synthesis of platforms

For the development of imine-based covalent organic frameworks, diverse platforms (also known as knots) applied to COFs construction have been used. To obtain novel COFs based on corrole, we picked some platforms. These platforms are assigned as 2D and 3D types based on the topology classification of COFs. Here, according to the functional moiety, they are divided into aldehyde-and amino-platforms.

Synthesis of amino-platform

In order to match the aldehyde-corrole, tetra(4-aminophenyl)methane (TAPM) was considered to further build a novel 3D COF. Several COFs based on aldehyde porphyrin and TAPM were reported in the literature during the recent years. [19][20][21] It is very interesting to try the design of a 3D COF from a corrole instead of a porphyrin. The synthesis of TAPM was modified according to the work published by Ganesan et al. 22 The tetra(4-aminophenyl)methane was synthesized according to the literature except for the hydrogenation step that was done using Pd/C-H2(gas). Scheme 14. Synthesis of 1,3,5,7-Tetra(4-formylphenyl)adamantane. 27 All the synthesis of COFs will be detailed in Chapter 3.

Precursors for MOFs

Different from COFs or POPs, MOFs are constructed via the coordination between metals and ligands. The coordination chemistry gives MOFs a modular nature, which allows for great synthetic tunability, affording both fine chemical and structural control. With creative synthetic design properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications. Tuning MOF precursor composition and manipulating conversion processes are two main strategies for chemical and structural control. Thus, we have used two methods to construct MOFs based on corrole: (1) synthesis of MOFs directly from corroles; (2) functionalization of MOFs with corroles.

Corroles precursors for MOFs

Inspired by the first example of corrole-based MOFs reported by Ma et al., 28 we first plan to repeat this MOF synthesis, then to insert cobalt and apply it for CO sorption. In the literature, they reported MOFs constructed from 5,10,15-tris(p-carboxyphenyl)corrole (H3TCPC) ligand and unprecedented D3d-symmetric 9-connected Zr6/Hf6 clusters. In order to obtain this MOF, 5,10,15-tris(p-carboxyphenyl)corrole was synthesized via several methods. We have used two different ways to synthesize 5,10,15-tris(p-carboxymethylphenyl)corrole which is the precursor for 5,10,15-tris(p-carboxyphenyl)corrole (Scheme 15). It was worthy to note that the yield for one pot synthesis is a slightly higher than the yield obtained when starting from dipyrromethane and aldehyde. Thus, we applied the one pot synthesis to large scale synthesis of 5,10,15-tris(pcarboxymethylphenyl)corrole. The targeted tris-COOH corrole was obtained in 90% yield. However, this last step was not totally reproducible. Thus, we have designed another strategy to synthesize tris-COOH corrole (Schemes 17 and 18). As shown in Scheme 16, 4-(benzyloxycarbonyl)benzaldehyde was obtain after benzylation of 4-formylbenzoic acid with benzyl bromide. 29 Then, we can prepared 5,10,15-tris(4-(benzyloxycarbonyl)phenyl)corrole by one pot synthesis procedure.

Under hydrogenation using Pd/C as catalyst, the tris-COOH-corrole was obtained in quantitative yield without traces of any impurity and in addition, the synthesis was shown to be very reproducible (Scheme 17). This reaction is the first example of the synthesis of a tris-COOH corrole by hydrogenation. After that, metalation of the 5,10,15-tris(pcarboxyphenyl)corrole with cobalt was followed. The cobalt 5,10,15-tris(pcarboxyphenyl)corrole was characterized by 1 H NMR (Fig. 4), hydrogen atoms from the aromatic positions were clearly shown around 9. 30 -8.20 ppm. Peaks around 9.26, 9.03, 8.84, 8.81 ppm represented the hydrogens on pyrrole while the shifts of hydrogens on phenyl centered around 8. 40 -8.27 ppm Hydrazine was added to raise the resolution of spectrum, however, due to an over excess, hydrazine was also found as an axial ligand coordinated to cobalt metal center of the corrole. The hydrazine replaced dimethyl sulfoxide and the 4 hydrogens shift appeared at -3.40 ppm. The free dimethyl sulfoxide showed normal chemical shift at 2.68 ppm in CD3OD.

The integration for hydrogen of DMSO should be 6 and the 7 H in Fig. 4 represents trace of DMSO as solvent from the metalation step. And on the 13 C NMR spectrum (Fig. 5), the peak at 40.4 ppm represented normal shift of free dimethyl sulfoxide.

Precursors for MOFs functionalization

In this part, we will present the synthesis of precursors which can be used to functionalize well known MOFs from the literature (reported without doping of corroles). For this extended work, preparations of precursors can be divided into two parts: (a) porphyrin for MOF construction; (b) corroles for further functionalization of MOF.

Porphyrin precursor for MOF construction

Here, we choose PCN-222 as the target to be potentially functionalized with corrole due to the high porosity, high stability and enough pore size for containing corroles. The Ni-porphyrin was synthesized exactly the same way as described in the literature. 30 In order to synthesize PCN-222, the Ni-tetracarboxyporphyrin was obtain according to Scheme 19. With an one pot synthesis from 4-carboxymethylbenzaldehyde, porphyrin 33 obtained for following steps. Then, metalation of porphyrin was carried to have porphyrin 34 followed by saponification to obtain porphyrin 35. Here, the metalation was conducted before saponification because it is more difficult to purify porphyrin 35 bearing 4 carboxylic acid groups. Scheme 19. Synthetic route to [5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinato]-Ni(II). [30][31][32]

Corroles precursors for further MOF functionalization

In order to incorporate corroles into PCN-222, several corroles containing carboxylic acid functions were designed and synthesized. All of ester corrole were synthesized starting from dipyrromethanes and 4-carboxymethylbenzaldehyde with MeOH/H2O/HCl conditions. The -COOH corrole were obtained by saponification or hydrolysis. Here, all corroles were functionalized with carboxylic acid group on the 10-meso-position of corrole (A2B-transcorrole). We have choosen three different moieties to functionalize the 5,15-meso-positions of the corrole macrocycle. The three moieties possess different electron withdrawing groups which may modulate the CO binding affinities. It is interesting to further compare the electronic effect of different moieties. For the corroles shown below (Scheme 20), the whole process started from the synthesis of dipyrromethane in high yields (85%, 96%, 95% respectively for compounds 8, 9, 10). All the reactions were catalyzed by MgBr2. Then, dipyrromethanes were Two methods can be used to functionalize PCN-222 with cobalt corrole: post-metallation or pre-metallation with cobalt. We have synthesized three different free base corroles and haved used them firstly in the post-functionalization of PCN-222 followed by cobalt metalation. To be different from previous methods, we have also selected and synthesized the cobalt complex Furthermore, we have also synthesized an A2B-corrole bearing two carboxylic acid moieties on at the 5,15-meso-positions (Scheme 24). The two carboxylic acid moieties may make it easier to functionalize PCN-222. We keep -CF3 at the 10-position of the corrole to be similar to the corroles previously used for the COFs.

Precursors for POPs

As another part of my PhD work, we were also interested in the synthesis of POPs based on corroles. As presented in Chapter 1, there are two examples of amorphous POPs based corroles. Among them, the POP constructed from diiodocorrole and tetra-alkyne platform through Sonogashira cross-coupling reaction is more attractive. 33 In order to have a more rigid 3D structure, we plan to use 1,3,5,7-tetrakis(4-iodophenyl)adamantane as a rigid platform and the di-alkyne corrole will be the linker. The synthesis of this corrole and platform was described below.

Synthesis of the corrole precursor

Different from the previous reported POP based on diiodocorrole and tetra-alkyne platform, 33 we have designed and synthesized di-alkyne corrole and tetra-iodo platform. It is easier to obtain di-alkyne corrole and tetra-iodo platform in few steps. The synthesis of dialkyne corrole was described in detail. Here, we tried two different strategies to obtain this corrole (Schemes 25 and 26). The main difference between these two processes is the order of the insertion of the alkyne groups either at the beginning or at the end of the synthesis. By comparing protocol and overall yield, the second method (Scheme 26) tended to be a better choice due to the simple and easy purification of the targeted corrole and high and almost quantitative yield when starting from 4-bromobenzaldehyde.

Synthesis of the adamantane precursor

Finally in order to design a POP with a more rigid platform, we were interested in the synthesis of 1,3,5,7-tetra(4-iodophenyl)adamantane. Firstly, 1,3,5,7-tetraphenyladamantane was obtained from 1-bromoadamantane and benzene (also used as solvent). The electrophilic substitution reaction between adamantane and benzene was carried under the catalyzis of tbutylbromide and aluminum chloride. Halogenation with iodine of adamantane 41 gave targeted 1,3,5,7-tetra(4-iodophenyl)adamantane 42 (Scheme 28). 34 Scheme 28. Synthesis of 1,3,5,7-tetra(4-iodophenyl)adamantane.

Conclusion

This chapter mainly presented the synthesis of the precursors involved in the construction of different porous materials: COFs, MOFs and POPs. The characterizations of these precursors are presented in the experimental part. In this chapter, we mainly synthesized different corroles.

The corroles can be used for COFs construction, MOFs functionalization and POPs construction. In the next chapter we are more particularly interested in the synthesis and characterization of new COFs.

Chapter 3

Synthesis of COFs based on cobalt corroles Chapter 3: Synthesis of COFs based on cobalt corroles

We have shown in Chapter 1 that cobalt corroles were capable of selectively adsorbing carbon monoxide. Our group has already published results concerning this property. [1][2][3] However, when we use monomer corroles complexes, the number of active sites of many cobalt corroles complex are much lower than expected. Generally, for these corroles, -stacking is likely to occur, being the predominant effect for non-porous solid state of corroles, thus making parts of cobalt sites unavailable for carbon monoxide binding. Moreover, after several cycles of CO sorption vs N2, O2 and CO2, a decrease of CO chemisorption was observed due to partial degradation of the corroles metal complexes. In order to get more efficient active species, we have been interested in the development of new porous materials based on cobalt corroles, and more particularly the covalent organic frameworks (COFs) which are the main subject of our research subject. The COFs are generally very stable and should allow the increase of the CO sorption volume compared to non-porous corrole solid. Up to date, there are only two examples of COFs based on corroles which are presented in chapter 1. 4,5 In this chapter, the study of new COFs based on cobalt corroles will be presented with their CO sorption properties.

Design of COFs for this project

In order to construct novel COFs, it is necessary to pre-design the structure and topology of COFs. As described in chapter 1, the topologies of COFs are decided by linkers and knots, which are also called systems (Cx + Cy). Through combination of diverse linkers and knots, different topologies can be achieved. According to different requirements of stabilities and applications, appropriate linkages can be used for many COFs. As presented before, two corrole-based COFs have been reported and both are based on an imine linkage (the most commonly encountered type of bonding among all COF linkages). Furthermore, in recent years, many examples of porphyrin-based COFs with imine linkage have been reported. [6][7][8][9] Corrole, as a member of the porphyrin family, is a very interesting macrocycle to further construct novel COFs via imine linkage.

Corrole, often A3 or trans-A2B substituted, is an C2 symmetric molecule bearing most of the time aryl groups at the 5,10,15-meso positions (Scheme 1). Reported by Ma and Zhang et al, 4,5 the T-shaped 5,10,15-tris(p-aminophenyl)corrole was applied to construct 2D COFs. We tried to reproduce these COFs but very quickly we realized that these COFs were not stable under the air. Thus, we planned to focus on the use of a more stable trans-A2B corrole with an attracting EWG -CF3 group for the construction of new COFs. With the C2 symmetric structure and reactive functions at the 5,15-meso positions, we wish to use corrole as linker for further COF construction. It is worthy to note that the corrole linker is in an unusual approximately Tshape (when A3) or linear shape (when A2B) due to the absence of a carbon at the 20-meso position compared to porphyrin. Thus, the topology of the targeted COFs will be in the system (C2 + Cy). According to the topology diagrams presented in Chapter 1, we can have (C2 + C3) and (C2 + Td) systems which represent 2D and 3D topologies, respectively. Furthermore, there are two reactive functions on corrole linker, thus, the knots used to react with the corrole should contain 3 or 4 reactive functions to construct either 2D layer or 3D network. In the literature, there are many examples of 2D COFs based on 1,3,5-triformylbenzene through imine linkage. For 3D COFs, tetraphenylmethane is generally considered as a great Td knot to construct 3D networks and it was usually functionalized into tetra(4-aminophenyl)methane or tetra(4-formylphenyl)methane.

For the rest of our work, we will use these last two precursors. As a reminder, all the precursors for COF constructions were described in Chapter 2.

Synthetic methods for the preparation of COFs

During the development of COFs synthesis, many synthetic methods have been reported by different groups: solvothermal synthesis, 10,11 microwave synthesis, 12,13 ionothermal synthesis, 14,15 mechanochemical synthesis, 16,17 interfacial synthesis 18,19 and synthesis under ambient conditions. 20,21 Among all these synthetic methods, the solvothermal approach has been widely used for the construction of high quality COFs. For the solvothermal synthesis, the reaction time, temperature, solvent condition and catalyst concentration are the most important factors to be considered in the preparation of highly crystalline COFs. 22 In this manuscript, among the different experiments available for COFs synthesis, solvothermal approach was mainly used.

Synthesis of COFs from aldehyde-corrole

The imine bond can be formed by the reaction of an aromatic amine and an aldehyde in the presence of organic acid or Lewis acid catalyst at high temperature (usually 120°C).

Considering the stability problems of certain corroles, we have proposed to build a COF from aldehyde-corrole which is comparatively more stable compared to an amino-corrole (Scheme 2). With amino functions, amino-corrole can be easier oxidized by O2. Checked by H NMR spectra and TLC monitoring, after a long time, amino-corrole have degradation: H NMR not clean anymore and many impurities showed on TLC. Scheme 2. Structures of aldehyde-and amino-corroles.

At the beginning of this PhD work, there were no examples of COFs based on corroles but COFs based on imine linked porphyrins have been widely reported. [23][24][25][26][27] Among these porphyrin COFs, aldehyde-and amino-porphyrins have been used as building blocks. Due to the similarity in structures and properties between corroles and porphyrins, it should be easier to optimize the synthetic conditions for corrole-based COFs. Thus, we were directly inspired by synthetic conditions of porphyrin COFs to further develop and obtain COFs based on corrole macrocycles (Table 1). acid, the solvents are required to possess some hydrophilicity to further allow water and acetic acid to take part in the imine formation well. Moreover, the mixture of water and acetic acid is very important to produce crystalline COFs. 34 In Scheme 3 below we present a first try to synthesize COF from the aldehyde-corrole linker 14 and the tetra(4-aminophenyl)methane platform 38 (Scheme 3). In order to obtain a complete and well organized structure, we used a 2 : 1 ratio (corrole 14 : platform 38) ratio of the starting precursors. All the reactions were carried in one solvent or mixtures of solvents using aqueous acetic acid as a catalyst. We have tried several different synthetic conditions, all synthetic condition optimizations for COF-1 are presented in Table 2.

Scheme 3. Synthesis of COF-1 from corrole 14 and platform 38. 3).

Table 3. Optimization of synthetic conditions for COF-1.

For the reactions in Table 3, corrole 14 (26.0 mg, 0.04 mmol, 2 eq) and platform 38 (7.60 mg, 0.02 mmol, 1 eq) were used again. During the reactions, experiments n°3 and 4 yielded powder like precipitates while n° 1, 2 and 5 yielded sponge like solid. Out of our expectations, none of them showed crystallinity while porphyrin-COFs analogs show good crystallinity. This could be assigned to the specific molecular structure of the corrole which is twisted line shape linker whereas the porphyrin precursor is more linear (Scheme 4). At least, the n°1 synthesized in 1,4-dioxane showed the highest BET surface area around 400 m 2 g -1 .

In order to check the reproducibility and obtain higher amount of samples for further CO binding test, synthetic condition n°1 of COF-1 was repeated on a larger scale (corrole 14 (72.8 mg, 0.11 mmol, 2 eq) and platform 38 (21.3 mg, 0.055 mmol, 1 eq)). The product was collected, washed and dried, yielding 20 mg of powder (21%) which is still quite low compared to most porphyrin-COFs. The d6 and adding hydrazine to increase resolution (experimental sections: part 6). The NMR spectrum exactly presented bis-CHO corrole and tetra-NH2 platform as linkers of COF-1. It was still amorphous and showed 430 m 2 g -1 of BET surface area which is close to the test n°1.

Considering the low yield of corrole 14 described in Chapter 2 and the low yield of COF synthesis, we concluded that it was not efficient to use bis-aldehyde corrole 14 as a linker to build COF.

Scheme 4. Structures of CHO-corrole and CHO-porphyrin.

Synthesis of COFs from amino-corrole

According to Table 1, imine COFs can be obtained from aldehyde-porphyrin, or aminoporphyrin monomer. The synthesis conditions for both are similar, thus we considered to apply 5,10-amino corrole as linker to synthesize COFs. In chapter 2, we described the synthesis of 5-(4-nitrophenyl)dipyrromethane and its A2B-corrole (bis-nitro corrole 15) with good yield (38%).

After that, the bis-amino corrole was obtained by reduction in H2 with palladium catalyst with a very good yield of 85%. Compared to the synthesis of aldehyde corrole, amino corrole can be synthesized in easier way and much higher yield, which make it a promising monomer for imine COFs. The following part focused on the application of amino corrole 16 as COFs linkers.

Synthesis of 3D-COF-Cor based on amino corrole

surface area is 500 m 2 g -1 (tube 1, yield 65%, mixture of n-BuOH/o-DCB/acetic acid (10:5:1, V/V/V)) (Table 4). The gel like solid in tube n°8 had the lowest BET surface area. After the optimization of the synthetic conditions for the 3D-COF-Cor, we selected the conditions of tubes n°1 for a synthesis on a larger scale. Corrole 16 (144 mg, 0.231 mmol, 2 eq) and platform 40 (50.0 mg, 0.115 mmol, 1 eq) were placed in a 50 mL Schlenk tube, charged with the mixture of n-BuOH/o-DCB/acetic acid (10:5:1, V/V/V in mL). The mixture was sonicated for 10 min and degassed via freeze-pump-thaw cycles. Then, the tube was sealed by a glass stopper. The mixture was heated for 3 days at 120°C. After collected, the large scale gives a good reproductible yield (64% versus 65% before). In order to check the reproducibility in larger scale, the reaction was repeated with 404 mg of corrole 16 and 104 mg of platform 40. After collected, the 3D-COF-Cor was given with a quite reproductible yield of 56% which means a possibility for practical application.

Until this step, the 3D-COF-Cor was successfully obtained and all the corroles inside this material are in their free base form. Desired COFs must have cobalt complexed corroles in order to be able to bind CO. These cobalt complexes were obtained via the metalation of the free base corroles in the synthesized 3D-COF-Cor (Scheme 6). In a flask was added 3D COF, followed by a solution of cobalt acetylacetonate in the mixture of DMSO and THF. The mixture was heated at 80 °C for 5 h under argon without stirring. After cooling down the solution, the suspension was centrifugated. After removing the supernatant, the solid was washed with THF several times to afford COF with cobalt corroles and DMSO ligand (3D-COF-CorCo-DMSO).

Then the 3D-COF-CorCo-DMSO was further washed with a solution of THF saturated with NH3(g) to afford 3D-COF-CorCo-NH3. The solid was then dried under vacuum. The 3D-COF-CorCo-NH3 was degassed under vacuum at 80°C to afford 3D-COF-Cor-Co (without ligands) which was used for further CO sorption tests. COFs precipitated in the tubes within 6 h. After collection, all of them tend to be powder like materials. The analyzes by PXRD and BET showed that the COFs synthesized in a mixture of mesitylene/n-BuOH present the highest crystallinity and BET surface area.

Table 5. Optimization of synthetic conditions for 2D-COF-Cor.

After the optimization step, we selected protocol n°4 because the COF obtained presented the best BET. A large scale synthesis of 2D-COF-Cor was performed in the mixture of n-BuOH/mesitylene/acetic acid (10:5:1, V/V/V in mL) with corrole 16 (231 mg, 0.37 mmol, 1.5 eq) and 1,3,5-triformylbenzene (40.0 mg, 0.25 mmol, 1 eq). We obtained the COF with a yield of 81% which is close to the optimized one (79%). To check reproducibility, we used twice as much of corrole 16 (462 mg). Once again, we obtained a highly reproducible yield of 81%. It was reported by Wang et al. that aniline can be used as the monofunctional competitor to modulate synthesis of COFs. 35 The introduction of aniline resulted in the enhanced crystallinity, surface area and pore volume, which is beneficial for the enrichment capability of the resulting COFs. Thus, we have also introduced aniline as modulator to improve crystallinity of 2D-COF-Cor. The quantity of aniline was introduced as 1. 5, 3, 15, 30, 45, 90 equivalents of the platform. With the addition of aniline, the crystallinity of 2D-COF-Cor reduced obviously (Fig. 1). When it came to 45 and 90 eq, isolated materials have shown to present no crystallinity.

After that, we were interested in the metalation of COF by Cobalt. For this, we used a similar procedure developed during the preparation of 3D-COF-Cor (Scheme 8). The only difference is the temperature control. When 2D-COF-Cor was metalated at 80°C, we observed a low metalation rate of 25% (checked by ICP). By increasing the temperature to 100°C, the cobalt metalation ratio can reach 84%. Like 3D-COF-CorCo, 2D-COF-CorCo was obtained by metalating the 2D-COF-Cor, exchanging DMSO ligand with NH3, then removing the NH3 units by heating at 80°C under vacuum. The two more shielded doublets at 7.87 and 6.99 ppm correspond to the protons on the 5-mesoand 15-meso-phenyl rings. The signals of the aryl platform appear at 7.42 and 7.68 ppm and no aldehyde function was observed. It turns out that the hydrazide form of 1,3,5-trisformylbenzene was obtained after the reaction with hydrazine, and only the CH=NNH2 function can be seen at 7.68 ppm. An average ratio of 1 corrole for 1 platform was determined by integration of the signals for 2D-COF-Cor, which is not close to the theoretical stochiometric ratio of 1.5 corrole for 1 platform. Since the imine formation is a reversible reaction, it is acceptable that one part of the corroles is lacking, which means that the material presents some corrole defects.

Concerning the 3D COF, the same 1 H NMR analysis was carried out (Fig. 3) and a similar ratio (1.1 corrole: 1 platform) was found, compared to a 2 : 1 ratio that is theoretically expected for a stochiometric defect-free material. Furthermore, the 1 H NMR spectra clearly show that there are no side products formed during the COF synthesis, which means that there is no occurring degradation of corrole-NH2. The results proved that the COFs structure helps to stabilize the corrole macrocycle.

Infrared Spectroscopy

The 2D-COF-Cor and 3D-COF-Cor clearly exhibit the formation of networks linked by C=N bonds that give a typical C=N stretching vibration at about 1610 cm -1 . 36,37 Indeed, the comparison of the IR spectra for the starting compounds e.g. 1,3,5-triformylbenzene and corrole-NH2 clearly shows the formation of the imine bond by the vibration at 1614 cm -1 for 2D-COF-Cor (Fig. 4). However, a peak at 1699 cm -1 attests to the presence of the terminal aldehyde groups in the resulting material, while the consumption of the amino groups, evidenced by the absence of the NH vibration around 3460 cm -1 is nearly complete. The sharp peak at 1323 cm -1 was tentatively assigned to the C-N stretching of the aromatic amine (Ph-N) groups which become bigger by the formation of conjugated imine linkages. The peaks at 1167

and 1128 cm -1 can be assigned to the C-N stretching of azomethine (C-C=N-C) groups. 38 All of these results further support the formation of the imine networks. The IR spectrum of 3D-COF-Cor also clearly shows the vibration of imine bond at 1610 cm -1 . The mirror difference from 2D-COF-Cor comes from the conjugation by the 2D platform (Fig. 5). We also compared the FTIR spectra of COFs-Cor and their corresponding cobalt complex counterparts (Fig. 6 and7). After the cobalt metalation of the corroles within 2D-COF-Cor, the characteristic peaks of 2D-COF-CorCo-DMSO and 2D-COF-CorCo-NH3 still match with that of the 2D-COF-Cor. After the metalation of 2D-COFs, the imine bond around 1614 cm -1 and the peaks in the range of 3500-2800 cm -1 remain visible. Interestingly, for COF-CorCo-DMSO (Fig. 6 and7), a weak peak around 1014 cm -1 was more prominent and can be assigned to the S=O stretching from the DMSO ligands. 39 When NH3 is coordinated to cobalt as the ligand, the peak at 3349 cm -1 in Fig. 4 clearly shows the N-H vibration for 2D-COF-CorCo-NH3. For 3D-COF-CorCo-NH3, the similar N-H vibration appears at 3352 cm -1 (Fig. 7). During the FTIR analysis of 2D-COF-CorCo-NH3 and 3D-COF-CorCo-NH3, a release of NH3 ligand were observed due to the high vacuum in the IR apparatus (Fig. 8). From Fig. 8, the N-H vibration from NH3 ligand was located at 3349 and 3352 cm -1 . PXRD analysis was also employed to determine the crystallinity of the synthesized COFs.

Powder X-ray diffraction

For 3D-COF-Cor, the PXRD indicates the amorphous nature of the material since we can observe no distinct diffraction features (Fig. 9). We assumed that the non-C2 symmetric structure of corrole makes it very difficult to form well-organized diamond-like 3D structure for 3D-COF-Cor. According to the literature, the 3D COF based on bifunctional C2 symmetric porphyrin also shows no crystallinity. 40 2D-COF-Cor shows a good crystallinity while 3D-COF-Cor is amorphous. The experimental PXRD pattern displayed in Fig. 10a shows three intense peaks at 2θ = 2.37°, 4.75° and 6.47° and a broad and weak peak at 24.5°, which are assigned to the (100), ( 200), ( 210) and

(001) lattice planes respectively, indicating long-range order in this framework. By comparison with already described 2D COFs, the morphology of the experimental patterns suggests that the 2DCOF-Cor is formed thanks to the eclipsed AA stacking mode. The Pawley-refined profile is highly consistent with the experimentally observed pattern, resulting in a good agreement factor (Rwp = 3.23 % and Rp = 2.27 %) and the reasonable profile difference (Fig. 10a). The eclipsed AA and AB stacking mode were presented in Fig. 10b and10d. The unit cell parameters were determined as a = b = 43.0 Å, considering the crystal structure as a hexagonal packing. In addition, the broad signal at 24.5° indicates a layer spacing between two adjacent corroles around 3.6 Å, which should be enough to allow the post-metalation of the COF with cobalt.

The structure model of 2D-COF-Cor was generated with the Materials Studio programs (Fig. 11). The initial unit cell dimension was set to the theoretical parameters. The Le Bail refinement was performed to optimize the lattice parameters iteratively until the Rwp value converges and the overlay of the observed with refined profiles shows good agreement. The atomic positions and total energies were then fully optimized using Forcite module of Materials Studio. The final crystal structure was then optimized using the Castep module of Materials Studio. The simulated layer spacing is 3.65 Å which is very close to the experimental pattern. This evidences that the macrocycles are still accessible despite their  stacking in the network.

The crystallinity of the metalated COF 2D-COF-CorCo was also investigated and it shows two main peaks at 2θ = 2.46° and 4.81° (Fig. 12). This result indicates that after inserting cobalt into the corrole macrocycles, 2D-COF-CorCo retains the same topology but a slight shrinking of the lattice parameters was observed. have been examined by Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X-ray Spectrometry (EDS). Regular plate-shaped nanoparticles with a narrow thickness in the range 400-800 nm and 1.0-1.5 m length have been obtained for both 2D-COF-Cor (Fig. 13a) and 2D-COF-CorCo-DMSO (Fig. 13b). Aside from those plate-shaped nanoparticles, granular crystallites bearing a sphere-like morphology are also present. Interestingly, the morphology and particle size remain similar after the insertion of cobalt into the corrole core (Fig. 13c). For 3D-COF-Cor and 3D-COF-CorCo-DMSO, a mixture of sphere-like and network-like nanoparticles were observed (Fig. 12b,13d). We can assume that the smallest particles tend to aggregate to form spherical nanoparticles with size 1.5-2.0 m, which are favored under the solvothermal conditions. This may be the reason why there are two different shapes of nanoparticles existing in 3D-COF-Cor and 3D-COF-CorCo-DMSO. We are also interested in mapping by EDS, the 2D/3D-COF-CorCo-DMSO taking cobalt and sulfur as the specific elements (Fig. 14). It was observed that sulfur and cobalt distributed evenly which means that the 2D/3D-COF-Cor was well metalated. Furthermore, we can also estimate the metalation ratio of cobalt by EDS. For each corrole unit, there is one -CF3 moiety.

If all corroles are metalated, the theoretical atomic ratio of cobalt to fluorine should be 0.33.

There are 7 points (Fig. 15) extracted to show the element analysis of 3D-COF-CorCo-DMSO in atom% (Table 6). The average atomic ratio for Co/F calculated from EDS mapping is 0.19 (Table 7). The cobalt metalation ratio is calculated as 58 %. For 3D-COF-CorCo, we obtain 4.59 % wt for Co (0.078 mmol g -1 ), against a theoretical value of 6.25 % wt, giving a 74% metalation ratio. Concerning the 2D-COF-CorCo-DMSO, 6 points (Fig. 16) were extracted (Table 8). The average atomic ratio for Co/F calculated from EDS mapping is 0.22 (Table 9). The cobalt metalation ratio is calculated as 67 %. And for 2D-COF-CorCo, we obtain 5.88 %wt for Co (0.099 mmol g -1 ), against a theoretical value of 7.45 %wt, giving a 78% metalation ratio. For 2D and 3D COF, the estimated cobalt metalation ratio from EDS is close to ICP. Due to the experimental error related to each of the analysis techniques, we considered that the metalation ratio calculated from EDS and ICP are concordant.

Thermogravimetric analysis

Thermal stability of the COFs materials was investigated by thermogravimetric analyses (TGA) conducted in the range of 20 °C to 900 °C with a heating rate of 10 °C min -1 under a synthetic air gas flow (Fig. 17). The TGA curves for these COFs materials exhibited almost no weight loss between 200 °C and 300 °C and only 3D-COF-CorCo and 2D-COF-Cor showed a ~3 % weight loss due to water adsorption by the porosity of the materials. A second step was clearly observed due to the calcination of the organic part of the materials that occurs in a higher temperature range. The calcination temperature was similar for both COFS, as it was observed in the range of 300 -650 °C for 2D-COF-Cor and 3D-COF-Cor, and a shorter range of 300 -460 °C was recorded for their metalated analogues. This result is clearly assigned to the destabilization of the corrole complexes compared to their respective free base. A plateau for 2D-COF-CorCo and 3D-COF-CorCo was reached at 9.0 % and 7.3 % respectively, and these values are in good agreement with the expected amount of cobalt (II) oxide (calcd for CoO:

9.5 % and 7.9 % according to ICP results). It is worthy of note that, when considering the corroles as fully metalated, the expected theoretical amount of cobalt(II) oxide were calculated as 10.5% and 8.8 %. From the TGA analyses, we then calculate the metalation ratios to be about 95 % and 92 % for 2D and 3D COF respectively, which is close to the EDS and ICP results.

Interestingly, the similarity of the thermograms between the free base COF in one hand and the metalated materials in the other hand clearly attests that despite their different topology, the 2D-COF and 3D-COF present the same stability. This result demonstrates that the thermal stability is dominated by both the nature of the linkages that connect corroles and platforms, and by the nature of the corrole itself, and that neither the crystallinity nor the topology of the framework are preponderant for the control of the thermal stability. 2D-COF-CorCo 9.0 9.5 95%

Gas sorption analysis

In order to analyze the permanent porosity of COFs, nitrogen adsorption-desorption measurements were carried out at 77 K for the four materials. Before gas adsorption measurements, all the COFs were heated under vacuum at 80 °C for at least 3 h until the pressure reached 5 × 10 -5 atm, making sure no solvent remained in the porous structure. 2D and 3D-COF-Cor both displayed nearly reversible type-I sorption behaviors (Fig. 18a and Fig. 19a).

For the 2D COF, the sorption curves showed high nitrogen uptake at low relative pressure (P/P0 < 0.2), which is a significant feature of microporous materials presenting also small mesopores of ~2 nm. The isotherm of 3D-COF-Cor exhibits a typical type-I morphology with reversible desorption step. In addition, the high uptake in the higher-pressure range (P/P0 > 0.95) is characteristic of intergranular sorption due to the presence of voids between the particles. After optimization of the COF synthesis with different reaction solvent systems and ratios, the highest BET surface area of 2D-COF-Cor and 3D-COF-Cor were obtained using the mixture n-BuOH/mesitylene/acetic acid (10:5:1, V/V/V) and mixture n-BuOH/o-DCB/acetic acid (10:5:1, V/V/V) respectively. The BET model was applied to the isotherm of 2D-COF-Cor and 3D-COF-Cor following the Rouquerol recommendations 41 to afford a BET surface area of 1141 m 2 g -1 and 489 m 2 g -1 , respectively. Further studies were conducted on 2D and 3D-COF-Cor produced from large scale synthesis, and each sample exhibited a BET surface area of 1266 m 2 g -1 and 484 m 2 g -1 respectively, which corresponds to the best optimization results and show the good reproducibility of the material synthesis. In the literature, the two reported COFs based on another free base corrole present a lower porosity 36,37 around 745 and 634 m 2 g -1 compared

to 1266 m 2 g -1 for the 2D-COF-Cor, first described in the present study. Our team 42 and others 43 also recently described a 3D POP based on corrole which gave a values of 645 and 416 m 2 g -1 compared to 484 m 2 g -1 for our 3D COF. The study of the metalated 2D and 3D-COF-CorCo also revealed a typical type-I isotherm with a sharp uptake at relative low pressure (P/P0 < 0.1), confirming their permanent porosity and the presence of microporosity with almost no mesoporosity, in contrary to the non-metalated materials. The BET surface areas were calculated to 638 and 489 m 2 g -1 , respectively. After metalation, the BET surface area of 2D-COF-CorCo displayed a sharp decrease due to the stacking of 2D layers and some shrinking of the framework, as previously revealed by PXRD analyses. These structural and porosity changes were triggered by the insertion of cobalt into the corrole. Nonlocal density functional theory (NLDFT) fitting of the adsorption branch for 2D-COF-Cor and 3D-COF-Cor displays pore size distributions with average pore widths of 6.1 Å, 10.4 Å, 23.5 Å and 5.7 Å, 11.6 Å, 25 Å, respectively (Fig. 18b and 19b). This reveals the presence of micropores and small mesopores, as well as irregularities, in their structures. But the mesoporous contribution is low for the 3D COFs, and it tends to vanish for the 2D COFs after the metalation. Furthermore, the BET surface area of 2D and 3D-COF-CorCo after CO adsorption cycles showed a slight decrease compared to those before the CO adsorption cycles. Apart from the basic analysis for BET surface area, we also made a comparison for the COF-Cor before and after kept in air for one month. In Fig. 20a, BET surface area of 3D-COF-Cor decreased from 489 m 2 g -1 to 101 m 2 g -1 after one month contact with air. But for 2D-COF-Cor, a slight decrease from 1141 m 2 g -1 to 1001 m 2 g -1 presented in Fig. 20b. The BET surface area is simply associated with the surface to volume ratio. The decrease may represent a collapse of internal structure which means 3D-COF-Cor is less stable than 2D-COF-Cor for micro-structure. 2D-COF-Cor presented a rigid structure against collapse. That is also associated with the high crystallinity of 2D-COF-Cor.

CO adsorption analysis

The CO adsorption properties of 2D-COF-CorCo and 3D-COF-CorCo were also evaluated along with the selectivity for CO vs. N2, O2 and CO2, which are the main components of the air, and the main potential interferents. As displayed in Fig. 21a and Fig. 21b, the adsorption isotherms for the gases were recorded at 298 K showing different adsorption volumes at 1 atm.

At first glance, the results indicate a good capacity and selectivity for CO adsorption 2D-COF-CorCo and 3D-COF-CorCo. At 1 atm, the two materials display a CO uptake of 32.2 cm 3 g -1 and 20.5 cm 3 g -1 at 298 K, respectively. Most importantly, for CO adsorption, both materials displayed a sharp uptake at a very low pressure (< 0.01 atm) which is dominated by the binding of CO molecules on the cobalt in the corrole through a chemisorption process. After saturation of all the accessible cobalt sites by CO molecules, the rest of the adsorption process was then led by physisorption due to the porosity of the materials. 2D and 3D-COF-CorCo also exhibit adsorption for N2, O2 and CO2 but only through physisorption, and no chemisorption was observed since no interaction occurred between these gases and cobalt corrole. 42,44 Among these gases, a high uptake of CO2 at 1 atm occurred through a physisorption process due to the stronger interactions between the surface of the materials and CO2. Up to now, only our team has reported porous materials based on cobalt corrole with a high affinity for CO at very low partial pressure, 42 which is a prerequisite to provide a good selectivity in gas mixture containing a low concentration of CO. In order to describe the CO adsorption process, the isotherm data were fitted with a triple-site Langmuir model while a single-site Langmuir model enabled the fitting of the CO2, N2 and O2 adsorption isotherms. The half saturation pressure for the selective sorption process was estimated to 0.65  10 -4 atm and 0.46  10 -4 atm for 2D-COF-CorCo and 3D-COF-CorCo, respectively. The two first components of the triple-site Langmuir model were assigned to the chemisorption of CO to the cobalt, which gives an estimation of chemisorbed atmosphere, which is mainly composed by N2, O2 and CO2. At zero pressure, the calculations gave very high selectivity values for CO over N2 (50129 and 22691) and O2 (5088 and 6800)

for 2D and 3D-COF-CorCo, respectively. These values correspond to the ratio of their corresponding Henry constants at zero pressure. In all cases, the selectivities decrease gradually with increasing pressure, but still remain higher than 11000 over N2 and 1400 over O2 at 1 atm.

Aside from the selectivity, 2D-COF-CorCo showed the highest capacity for CO at low pressure (P < 0.1 atm) compared to either 3D-COF-CorCo or the recently reported POPs based on cobalt corrole. 42 This result should be assigned to the better accessibility of the cobalt site in 2D-COF-CorCo for CO binding owing to the better structuration and organization of the pore channels.

Accordingly, it is considered that the selectivity of 2D/3D-COF-CorCo for CO over N2, O2 and CO2 is far higher than those reported for other porous materials like MOFs and POPs. 42,47,48 Despite the lower selectivity for CO over CO2 compared to other gases, the CO/CO2 selectivity is still high (> 20) at 1 atm even with a CO/CO2 ratio of 0.01/99.99. However, in a real atmosphere containing 400 ppm of CO2, only the selectivities at low partial pressures of CO2 must be considered for the targeted application as CO sensors. Furthermore, the reversibility of the materials for CO was studied by recording successive CO adsorption cycles after degassing at 80 °C between each sorption cycle (Fig. 22 and23). The results showed that after 4 cycles, both COFs gave satisfactory reversibility results. The slight decrease of CO adsorption between the first and forth cycle could be assigned to a partial collapse of the structures and porosities, as shown by the decrease of their BET surfaces after 4 cycles (Fig. 18a and19a). The reversibility study of the CO adsorption for 2D and 3D-COF-CorCo were also carried out by FTIR spectroscopy in transmission mode using KBr pellets of COFs under either a CO atmosphere or under vacuum (Fig. 24 and 25). Before exposure to CO, the activation of these materials was achieved under vacuum at 20 °C in order to remove the coordinated ammine on the cobalt corrole. After 24 h, the ammine ligands were removed since the characteristic stretching vibration of NH3 totally vanished. Then, the KBr pellet was placed in a CO atmosphere (1 bar) for 1 h and the chamber was purged for 5 min with nitrogen to remove extra CO (Fig. 24a). For 2D-COF-CorCo, an intense vibration band at 2044 cm -1 appeared and this frequency value is characteristic to CO bounded to a metal ion via the carbon atom. 42 The lower value compared to free CO (2143 cm -1 ) is assigned to the sigma donation of CO from the carbon orbital into the empty dz2 orbital of cobalt. The electron density can also be -backdonated from d orbitals of the cobalt to -antibonding orbitals of CO. [49][50][51] This π-backdonation tends to weaken the CO bond vibration leading to a red-shift of the CO stretching frequency with respect to free CO (2143 cm -1 ), as already observed in a Co(III) corrole series. 42,44 Successive spectra were then recorded after exposure the chamber to vacuum (2 mbar). As displayed in Fig. 24b, a constant decrease of the bonded CO vibration intensity was observed over time under vacuum. After 90 h, the CO vibration almost disappeared and the intensity didn't change any more, which means that there was no more CO coordinated on cobalt corroles.

However, the half-desorption time was rather short since it was estimated to 30 min (Fig. 26).

These data clearly reveal that CO adsorption in the COFs involved the coordination of the gaseous molecules on the cobalt atom according to a reversible process. For 3D-COF-CorCo, similar results for the reversible process were observed (Fig. 27). The only difference is that it took only 36 h to remove all the bonded CO to the cobalt corroles.

However, both of them showed a fast CO desorption in the first hour which indicated a fast and reversible CO desorption. The reversibility for CO binding on 2D and 3D-COF-CorCo was studied by carrying out two cycles of adsorption and desorption of CO, and monitored by FTIR.

For 2D-COF-CorCo, after 80 h vacuum, the CO was desorbed until it reached an equilibrium but it did not desorb completely (Fig. 24b). This could be caused by the -stacking structure of 2D COF, which makes it more difficult to release CO. For 3D-COF-CorCo, the first cycle of sorption and desorption of CO presented the same behavior as for 2D-COF-CorCo. However, for the second cycle the desorption of CO was total (Fig. 28). These results showed good reversibility of CO binding and desorption for 2D and 3D-COF-CorCo. The half-desorption time was rather short since it was estimated to 45min (Fig. 29) means a fast desorption of CO and good reversibility. We carried out 9 tests by mainly varying the solvents. In all the tubes, the solvent was at the end colorless which means that the corrole dyes were consumed. All of the yields were mostly greater than 90%. It was therefore expected, like 2D-COF-Cor, to have high crystallinity and BET surface area. However, the various tests led to amorphous materials and with a low specific surface area. This could be explained by the fact that the product precipitates too fast.

And if the irreversible enol ketone tautomerism occurs too soon, the framework doesn't have a crystal structure because it cannot go back. We have also synthesized a truxene unit functionalized by three aldehyde functions (see chapter 2, part 2.1.2.2) in order to use it as a platform with the amino corrole 16 (Scheme 11).

This moiety has the particularity of being flat, we hope to improve the crystallinity of COF. The optimization synthesis (variation of solvent mixtures) is showed in Table 9. For each of the three trials, we had the same problem. During the washing of materials, a release of the corrole was observed (green color of the solvent characteristic of the corrole). It is deduced from this that this COF tends to degrade, it is therefore not very stable. It could be assigned to the special structure of truxene. With the long chains at vertical direction on two sides, it is very difficult for truxene to have 2D layer accumulation due to the space hinder (Fig. 30). Compared to 2D-COF-Cor which has - stacking between layers, COF-3 is less stable and presents no crystallinity. and their cobalt complexes. The resulted porous 2D-COF-Cor showed good crystallinity with a hexagonal packing and an AA arrangement. Interestingly, the crystallinity and permanent porosity were preserved after post-metalation with cobalt. In contrast, three dimensional 3D-COF-Cor showed a microporous but amorphous structure. Both corrole-based materials also show a high surface area that reached 1266 m 2 g -1 in the case of the 2D COF. In contrast, 3D

COF showed a lower BET surface area of 484 m 2 g -1 . Post-metalation allowed us to insert cobalt into the corrole macrocycle almost quantitatively in order to obtain the targeted COFs-CorCo for further CO adsorption. Both of them exhibited outstanding affinities and selectivities for CO binding over N2, O2 and CO2. It is also worth noting that the adsorption of CO for COFs-Co is reversible through at least 4 cycles, even if a slight decrease of CO uptake was observed.

However, the CO adsorption for both COFs tend to be stable after 4 cycles since it did not decrease anymore after 4 cycles. We have also shown that the combination of crystallinity and regular porosity of the framework allow a better accessibility of the cobalt corrole for gas binding. Desorption of CO was studied by FTIR that showed that both COFs exhibit a fast desorption of CO with a half-desorption time estimated to 30 min. This result is a real prerequisite to build sensors with fast response. These results demonstrate that the combination of cobalt corroles and COF materials provides an attractive strategy for the selective CO capture, and our work are currently in progress for developing new gas sensor technologies featuring great potential of applications.

General conclusion and perspectives

The objective of this thesis was to develop porous materials based on cobalt corroles in order to further deposit them on SAW sensors to achieve highly sensitive and selective carbon monoxide detectors. Among various porous materials, we focused on covalent organic frameworks (COFs), which typically possess high permanent porosities, large surface areas and excellent thermal stabilities. Given these ideal characteristics, we aimed to design and synthesize many COFs with different structures or topologies.

First, we successfully prepared aldehyde and amino functionalized corrole linkers and a variety of platforms which were used to form the desired COFs via imine condensation. For the first tests, we used bis-aldehyde corrole 14 as a linker and tetra(4-aminophenyl)methane 38 as a platform to build COF-1. Given the low yield of bis-aldehyde corrole and COF-1, it was difficult to produce a large quantity of COF-1 for further analysis and application. Thus, we selected bis-amino corrole 16 as a linker to synthesize COFs. Several platforms such as tetra(4formylphenyl)methane 40, 1,3,5-triformylbenzene, 2,4,6-trihydroxybenzene-1,3,5tricarbaldehyde, 5,5,10,10,15,15-Hexabutyl-2,7,12-triformyltruxene 48 and 1,3,5,7-tetrakis-4-formylphenyladamantane 43 were applied with the amino corrole linker for COF synthesis, and, in each case, we optimized the synthetic conditions before producing the materials on a larger scale. With the optimization and characterization by PXRD and BET measurements, we have been able to find the best reaction conditions for synthesis of the desired COFs.

With tetra(4-formylphenyl)methane 40 and 1,3,5-triformylbenzene, we synthesized two materials named 3D-COF-Cor and 2D-COF-Cor, respectively. 3D-COF-Cor showed normal BET surface area as compared to the reported POP-Cor as well as an amorphous structure. 2D-COF-Cor presented much higher porosity and higher crystallinity. Furthermore, these two materials could be reproduced in good yields on a larger scale. Next, cobalt metalation for corrole units in the COFs was carried out to obtain materials suitable for testing CO binding.

The cobalt metalation of 3D-COF-Cor and 2D-COF-Cor were carried out with cobalt acetylacetonate in a mixture of DMSO and THF at 80°C and 100°C, respectively. The difference in temperature required for metalation was attributed to differences in topology between the two COFs, where 2D-COF-Cor presented a 2D layer stacking structure which is more difficult for cobalt insertion into the corrole. In the metalated COFs, a DMSO molecule is coordinated to the cobalt center and is difficult, yet necessary to remove for further CO binding. Thus, we exchanged the DMSO ligand with two NH3 molecules and NH3 can be removed easily by smoothly heating at 80°C under vacuum. This series of reaction steps afforded 3D-COF-CorCo and 2D-COF-CorCo without any ligand on the cobalt center, a material suitable for CO binding studies. During the CO sorption tests, 3D-COF-CorCo and 2D-COF-CorCo presented high selectivity and sensitivity for CO. However, 2D-COF-CorCo showed a higher affinity for CO as compared to 3D-COF-CorCo. Thus, it was concluded that 2D-COF-CorCo could be a promising material for sensor application.

In the following part, we also tried to synthesize COF-2, COF-3 and COF-4 based on 2,4,6trihydroxybenzene-1,3,5-tricarbaldehyde, 5,5,10,10,15,15-Hexabutyl-2,7,12-triformyltruxene 48 and 1,3,5,7-tetrakis-4-formylphenyladamantane 43, respectively. Among them, COF-2 was synthesized by imine condensation and keto-enol tautomerism. With these two steps, COF-2 can be stabilized by the irreversible enol form to display higher resistance to acidic or basic environment. However, COF-2 presented lower BET surface area along with poor crystallinity as compared to 2D-COF-Cor, thus, more optimization will have to be done to obtain the best COF-2. COF-3 was found to be unstable with constant degradation, an observation attributed to the long chains on the truxene which disrupt the - stacking between the 2D layers. Without rigid nanoparticles, COF-3 started to degrade rapidly. COF-4 possessed a similar structure as that of 3D-COF-Cor. Indeed, COF-4 presented a similar BET surface area and an amorphous structure as 3D-COF-Cor, but we expected that the rigid adamantane platform would improve the porosity and crystallinity of COF-4. However, measurements revealed that the characteristics of COF-4 were not improved from 3D-COF-Cor.

Since we already obtained 3D-COF-CorCo and 2D-COF-CorCo, for the next step, we planned to apply them on a SAW sensor. With the surface covered by silicon or silicon dioxide, 3-aminopropyltriethoxysilane (APTES) was considered to be a perfect coupling agent as it allows for further attachment of molecules through its terminal amines and exhibits selfassembled mono-layers. In addition, silanization is a reaction often used to attach APTES onto various surfaces. This reaction involves the initial hydroxylation of silicon dioxide, or glass, with subsequent hydrolysis of the APTES ethoxy groups with ethanol as the leaving group, resulting in an aminopropyl-terminated surface. This amino-functionalized sensor should be easily coated with our imine COFs, and thus it is a promising route to apply COFs on a SAW sensor.

In chapter 2, we also synthesized many other corroles which could potentially be used to synthesize metal-organic frameworks (MOFs) and porous organic polymers (POPs In parallel to CO detection, we could also apply the COFs for other applications by inserting different metals in the corrole linkers. Since we can easily repeat the synthesis of COFs with free base corrole on a large scale, it gives a rich platform to test the insertion of other metal ions such as Mn, Fe, Cu, Ga… These metal-derivatives could be applied in many areas of research such as catalysis, anticancer drugs, photodynamic therapy and hydrogen evolution… Thus, COFs based on corroles can be seen as promising materials for various applications.

4-(4,4-Dimethyl-2,6-dioxan-1-yl)benzaldehyde (2) 3 The procedure from literature was slightly modified. A 1.6 M solution of n-BuLi in hexane (120 mL, 0.19 mol, 1.2 eq) was slowly added to a degassed solution of 1 (43.0 g, 0.16 mol, 1 eq) in dry THF (500 mL) at -78°C under argon. When the addition was completed, the solution was stirred for 30 min at -78 °C then allowed to warm to 0 °C (over 1 h) and cooled again to -78 °C.

Dry DMF (25.0 mL, 0.32 mol, 2 eq) was then added and the resulting mixture allowed to warm to 0 °C (over 1 h). An aqueous 1 M HCl solution (200 mL) was added and the mixture was concentrated. The aqueous layer was extracted twice with DCM. The combined organic layers were washed with water, dried (MgSO4), and evaporated to dryness. The crude compound was purified by column chromatography (Silica, DCM/heptane = 1:1), giving compound 2 as colorless crystals.

Yield: 22.0 g (63%) The procedure from literature was slightly modified. In a round bottom flask, 4bromobenzaldehyde (5.55 g, 30.0 mmol, 1 eq), PdCl2(PPh3)2 (421 mg, 0.06 mmol, 2 mol%),

and CuI (228 mg, 1.20 mmol, 4 mol%) were dissolved in dry THF (30 mL). Et3N (6.24 mL, 45.0 mmol, 1.5 eq) and trimethylsilylacetylene (4.47 mL, 31.5 mmol, 1.05 eq) were added and the reaction mixture was stirred overnight under argon at room temperature. When the reaction is completed, the volatiles were removed under reduced pressure. The obtained crude product was purified by column chromatography (silica, heptane), giving compound 4 as colorless powder. To keep it stable, the compound was stored under argon atmosphere.

Yield: 6.01 g (99%)

1 H NMR (500 MHz, CDCl3) δ 10.00 (s, 1H), 7.81 (d, J = 8.5 Hz, 2H), 7.60 (d, J = 8.5 Hz, 2H), 0.27 (s, 9H).

Synthesis of dipyrromethane derivatives as precursors of corroles

General procedure for the synthesis of dipyrromethanes 6

A: In an Erlenmeyer were added aldehyde (30.0 mmol) and pyrrole (160 mL, 2.36 mol) and the mixture was degassed by a stream of nitrogen for 10 min. TFA (258 µL, 3.0 mmol) was added, and the mixture was stirred for 1 h at room temperature. The mixture was treated with powdered NaOH (4.0 g, 0.10 mol), stirred for 1 h and then filtered on celite. The filtrate was concentrated, and the pyrrole was recovered. Traces of pyrrole were removed by dissolving the oil in DCM and the organic fraction was washed three times with water then evaporated and dried.

B:

In an Erlenmeyer were added aldehyde (50.0 mmol) and pyrrole (347 mL, 5.00 mol) and the mixture was degassed by a stream of nitrogen for 10 min. MgBr2 (4.60 g, 25.0 mmol) was added, and the mixture was stirred for 1.5 h at room temperature. The mixture was treated with powdered NaOH (10.0 g, 0.25 mol), stirred for 1 h and then filtered on celite. The filtrate was concentrated, and the pyrrole was recovered. Traces of pyrrole were removed by dissolving the oil in a mixture of ethyl acetate and heptane (400 mL, 1:1) and the volatiles were removed. The solid was then dissolved in DCM and filtered on short plug of silica.

C:

In an Erlenmeyer were added aldehyde (35.0 mmol) and pyrrole (347 mL, 5.00 mol) and the mixture was degassed by a stream of nitrogen for 10 min. InCl3 (1.11 g, 5.00 mmol) was added, and the mixture was stirred for 1.5 h at room temperature under argon.

The mixture was treated with powdered NaOH (6.00 g, 0.15 mol), stirred for 1 h and then filtered on celite. The filtrate was concentrated, and the pyrrole was recovered. The traces of pyrrole were removed by dissolving the oil in a mixture of ethyl acetate and heptane (400 mL, 1:1) and the volatiles were removed. The solid was then dissolved in DCM and filtered on short plug of silica.

5-(4-Nitrophenyl)dipyrromethane (6) 8

The dipyrromethane 6 was obtained according to the procedure described above using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, 4nitrobenzaldehyde (7.56 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. The further recrystallization gives yellow-brown powder.

Yield: 12.0 g (90%)

1 H NMR (500 MHz, DMSO-d6) δ 10.67 (s, 2H), 8.17

5-(4-Carbomethoxyphenyl)dipyrromethane (7)

The dipyrromethane 7 was carried out by a modification of the procedure reported by Laha et al. 6 , using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, 4-carbomethoxybenzaldehyde (8.21 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. Further recrystallization gives colorless powder.

Yield: 22.8 g (81%) The synthesis of dipyrromethane 8 was carried out by a modification of the procedure reported by Laha et al. 6 , using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, benzaldehyde (5.31 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. Further recrystallization gives white powder.

Yield: 18.8 g (85%) Dipyrromethane 10 was obtained according to the procedure described above using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, 2,6dichlorobenzaldehyde (8.75 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. Further recrystallization gives colorless powder.

Yield: 13.8 g (95%)

5-(4-Bromophenyl)dipyrromethane (11) 10

Dipyrromethane 11 was obtained according to the procedure described above using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, 4bromobenzaldehyde (9.25 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. Further recrystallization gives colorless powder.

Yield: 14.5 g (96%)

5-(4-(Trimethylsilylethynyl)phenyl)diyrromethane (12) 11

Dipyrromethane 12 was obtained according to the procedure described above using general procedure for the synthesis of dipyrromethanes (Method C). For the reaction, compound 4 (10.1 g, 50 mmol, 1 eq) and freshly distillated pyrrole (495 mL, 7.14 mol, 143 eq) were used.

Further recrystallization gives colorless powder.

Yield: 13.9 g (87%)

Synthesis of corroles

General procedure A: synthesis of corroles from dipyrromethane 12 Dipyrromethane (10.0 mmol, 1 eq) and aldehyde (5.0 mmol, 0.5 eq) were dissolved in 500 mL of methanol. Then, a solution of HCl (36%, 25.0 mL) in H2O (500 mL) was added, and the reaction mixture was stirred at room temperature for 2 hours. The mixture was extracted with chloroform and the organic phase was washed three times with water, dried and completed to 1.50 L. p-Chloranil (1.5 eq) was added and the reaction mixture was stirred overnight at room temperature protected from light and the solution was evaporated. The resulted compound was purified by column with DCM as eluent. Then the crude compound was recrystallized with THF and heptane to afford crystal power. The solid was filtered and dried by vacuum.

General procedure B: one pot synthesis of A3 free-base corrole 12 To a solution of aldehyde (1 eq, 20 mmol) in methanol (400 mL) in an erlenmeyer was added pyrrole (2 eq). Then an aqueous solution of hydrochloric acid was added (8.50 mL of concentrated HCl in 400 mL of distilled water). The mixture was protected from light and stirred during 3 hours. The solution was diluted with chloroform (300 mL). The organic phase was washed twice with water, dried over magnesium sulfate and completed to 1200 mL with chloroform. p-Chloranil was added (1 eq, 20 mmol) and the reaction mixture was stirred, protected from light, during overnight at room temperature and the solution was evaporated.

General procedure C: synthesis of carboxylic acid corroles by saponification 13 According to the procedure reported by Yadav et al., a modification was conducted for our experiments. For the saponification of corrole with mono-carboxymethyl, corrole (1 mmol, 1 eq) and NaOH (30 mmol, 30 eq) were added into the mixture of EtOH (95 mL) and H2O (5 mL) under argon. The mixture was stirred and heated to reflux for 12 h. The reaction was monitored by mass spectrometry. After cooling, the mixture was acidified by 1M HCl solution monitored by pH. Until no precipitate appears, the crude compound was collected by centrifugation, washed with H2O and dried under vacuum, giving pure compound. For the other corroles containing two or three carboxymethyl functions, the amount of NaOH were adjusted to 60 eq or 90 eq. General procedure B was also conducted for corrole 13 but the reaction didn't work.

5,15-Di(4-formylphenyl)-10(4-trifluoromethylphenyl)corrole (14)

The corrole 14 is not described. The previously isolated mixture of corrole 13 and partially and/or totally deprotected corroles (212 mg) was dissolved in the mixture of THF (20 mL), H2O 5, 149.3, 141.2, 140.4, 139.9, 138.9, 136.1, 135.1, 134.9, 134.2, 132.1, 126.2, 125.5, 124.7, 123.9, 123.5, 121.5, 114.9, 113.6, 105.1. UV-vis (DCM): max (nm) ( 10 -3 L mol -1 cm -1 ) 433 (88.0), 587 (18.1), 628 (14.6), 661 (10.1), 700 (2.1).

FTIR (KBr, cm -1 ): 1699 (C=O aldehyde). 7, 147.5, 140.8, 140.1, 136.5, 135.4, 135.3, 132.0, 129.9, 126.4, 126.1, 123.6, 123.6, 123.2, 121.3, 115.4, 114.0, 113.9, 103.7.

19 F NMR (470 MHz, DMSO-d6, 10 L Hydrazine) δ -60.12 (s, 3F). UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 433 (67.7), 557 (8.0), 629 (11.5), 663 (12.9), 720 (13.4).

MS (MALDI-TOF

Elementary analysis (%): calculated for C38H27F3N6  0.5 H2O: C 71.31, H 4.43, N 13.10; found: C 71.84, H 4.32, N 12.94.

FTIR (cm -1 ): 3368 (N-H).

5,10,15-Tris(4-(benzyloxycarbonyl)phenyl)corrole (18)

The corrole 18 is not described. Corrole 18 was synthesized according to the described general procedure B. For the reaction, aldehyde 3 (9.60 g, 40.0 mmol, 1 eq) and freshly distillated pyrrole (5.36 g, 80.0 mmol, 2 eq) were used. The collected crude compound was purified by short plug (silica, DCM) and recrystallized from THF/MeOH, giving purple crystals.

Yield: 2.18 g (18%) UV-vis (DCM): max (nm) (10 -3 L mol -1 cm -1 ) 428 (106.4), 585 (18.3), 622 (14.7), 660 (10.2).

FTIR (KBr, cm -1 ): 1718 (C=O ester).

5,10,15-tris(4-carboxylphenyl)corrole (19) 16

To obtain reported corrole 19, two strategies were designed and carried out.

A. Saponification of carboxymethyl corrole 17

According to general procedure C. Corrole 17 (1.28 g, 1.83 mmol, 1 eq) and NaOH (6.58 g, 164 mmol, 90 eq) were used in the reaction along with EtOH (190 mL) and H2O (10 mL). UV-vis (DCM): max (nm) (10 -3 L mol -1 cm -1 ) 428 (105.6), 585 (17.3), 623 (14.4), 660 (11.1), 700 (6.9) nm FTIR (KBr, cm -1 ): 2998 (broad peak, OH carboxyl), 1672 (C=O carboxyl).

5,15-Diphenyl-10-(4-carboxymethylphenyl)corrole (21) 17

The corrole 21 is described. 17 Corrole 21 was synthesized according to the described general procedure A above. For the reaction, dipyrromethane 8 (2.22 g, 10.0 mmol, 1 eq) and 4carboxymethylbenzaldehyde (821 mg, 5.0 mmol, 0.5 eq) were used. The crude compound was collected and recrystallized, giving purple powder.

Yield: 1.23 g (42%) 6, 147.4, 141.1, 139.9, 139.7, 136.1, 135.2, 135.0, 131.6, 128.5, 128.1, 127.6, 127.6, 125.6, 122.6, 116.3, 115.9, 108.6, 52.4. The corrole 22 is described. 17 Corrole 22 was obtained according to the described general procedure C above. For the reaction, corrole 21 (750 mg, 1.28 mmol, 1 eq) and NaOH (1.54 g, 38.4 mmol, 30 eq) were used. The crude compound was collected and recrystallized, giving purple solid.

MS (MALDI

Yield: 651 mg (89%) 3, 146.0, 142.1, 140.8, 139.9, 136.2, 135.9, 134.5, 133.7, 131.7, 127.5, 127.3, 125.9, 125.0, 124.3, 121.0, 114.5, 113.2, 106.6. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 389 (45.8), 568 (8.7).

MS (MALDI

FTIR (KBr, cm -1 ): 2996 (broad peak, OH carboxyl), 1700 (C=O carboxyl), 1010 (S=O DMSO).

5,15-Dipentafluorophenyl-10-(4-carboxymethylphenyl)corrole (24) 18

Corrole 24 was obtained according to general procedure A described above. For the reaction, dipyrromethane 9 (3.12 g, 10 mmol, 1 eq) and 4-carboxymethybenzaldehyde (821 mg, 5 mmol, 0.5 eq) were used. The crude compound was collected and recrystallized, giving purple solid.

Yield: 550 mg (14%) 13 C NMR (125 MHz, DMSO-d6) δ 167. 3, 147.2, 146.3, 145.2, 143.0, 140.9, 139.0, 138.9, 137.1, 137.0, 134.8, 129.6, 128.6, 127.6, 126.0, 117.7, 114.1, 112.4, 77.2, 52.5. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 411 (148.0), 424 (132.4), 566 (24.3), 612 (14.5), 642 (5.9).

FTIR (KBr, cm -1 ): 1706 (C=O ester).

5,15-Dipentafluorophenyl-10-(4-carboxylphenyl)corrole (25) 18

Corrole 25 was obtained according to a method previously described in the literature. 18 Corrole 24 (400 mg, 0.52 mmol) was dissolved in a mixture of AcOH (10 mL), TFA (5 mL) and 5% aqueous H2SO4 (3.4 mL). The reactional mixture was protected from light and stirred at 100°C under argon. After 48 h, the mixture was cooled down, and NaHCO3 solution (5% aq) was carefully added. The mixture was extracted with CHCl3 and organic layer was dried by Na2SO4.

The crude compound was purified by column chromatography (Silica gel, DCM:MeOH = 100:5), giving pure product.

Yield: 345 mg (88%) 13 C NMR (125 MHz, MeOD-d4) δ 176. 1, 148.4, 147.7, 146.7, 142.6, 142.1, 140.0, 137.9, 137.2, 135.3, 134.0, 128.6, 127.0, 125.1, 122.1, 118.3, 117.4, 111.3, 95.4. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 411 (113.9), 424 (101.6), 566 (18.7), 612 (11.4), 642 (4.8).

FTIR (KBr, cm -1 ): 2923 (broad peak, OH carboxyl), 1685 (C=O carboxyl). Corrole 26 was obtained according to general procedure A described above. For the reaction, dipyrromethane 10 (2.91 g, 10 mmol, 1 eq) and 4-carboxymethybenzaldehyde (821 mg, 5 mmol, 0.5 eq) were used. The crude compound was collected and recrystallized from CHCl3/MeOH, giving purple solid.

Yield: 1.20 g (33%) 13 C NMR (100 MHz, DMSO-d6, 10 L Hydrazine) δ 167. 1, 149.8, 140.6, 140.4, 139.4, 137.8, 135.5, 134.8, 132.2, 130.4, 127.9, 127.5, 127.4, 124.2, 124.0, 120.2, 115.3, 107.3, 106.5, 52.4. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 410 (138.8), 427 (114.8), 569 (22.6), 608 (14.0), 638 (4.9).

MS (MALDI

FTIR (KBr, cm -1 ): 1702 (C=O ester). 13 C NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 171. 40, 145.48, 140.78, 139.57, 139.46, 137.80, 136.83, 135.38, 133.61, 131.95, 130.33, 127.90, 127.37, 124.65, 123.60, 119.90, 115.06, 107.88, 106.82. 3, 143.1, 140.5, 140.0, 136.1, 135.1, 133.9, 132.1, 128.5, 126.8, 126.3, 125.7, 124.1, 123.9, 123.5, 123.5, 121.6, 114.9, 113.8, 105.0. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 435 (100.7), 468 (41.4), 560 (7.4), 589 (7.4), 645 (13.2), 699 (24.1).

MS (MALDI

FTIR (KBr, cm -1 ): 2962 (broad peak, OH carboxyl), 1689 (C=O carboxyl).

5,15-Di(4-(trimethylsilylethynyl)phenyl)-10-(4-trifluoromethylphenyl)corrole (31)

Corrole 31 was synthesized through two synthetic pathways.

A. Sonogashira cross-coupling reaction

Corrole 30 (1.00 g, 1.33 mmol, 1 eq) and PdCl2(PPh3)2 (382 mg, 0.544 mmol, 0.4 eq) were placed in a round bottom flask, followed by vacuum and argon cycles. Dry THF (100 mL), TEA (37.5 mL) and (trimethylsilyl)acetylene (756 L, 5.32 mmol, 4 eq) were added under argon. The mixture was heated and stirred at 70°C for 12 h. The solvents were removed and residues were purified by column chromatography (Silica, DCM: heptane = 3:7), recrystallized from DCM/heptane, giving pure compound.

Yield: 397 mg (38%)

B. General procedure A from dipyrromethane

Corrole 31 was synthesized according to general procedure A described above. For the reaction, dipyrromethane 12 (3.18 g, 10 mmol, 1 eq) and 4-trifluoromethylbenzaldehyde (870 mg, 5 mmol, 0.5 eq) were used. The crude compound was collected and recrystallized from DCM/ heptane, giving purple solid.

Yield: 408 mg (33%) 13 C NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 149. 1, 142.8, 140.5, 140.3, 139.8, 135.9, 135.0, 134.8, 132.1, 131.1, 127.2, 125.3, 124.3, 123.5, 121.6, 119.3, 115.4, 112.7, 105.7, 84.2, 81.3, 1.9. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 424 (136.2), 584 (22.8), 624 (20.4), 652 (12.9).

MS (MALDI

FTIR (KBr, cm -1 ): 2158 (CC), 838 (Si-C).

5,15-Di(4-ethynylphenyl)-10-(4-trifluoromethylphenyl)corrole (32)

Corrole 31 (600 mg, 0.762 mmol, 1 eq) was placed in a round bottom flask followed by vacuum and argon cycles. 50 mL of dry DCM was added under argon and the mixture was stirred for 5 min to dissolve all the corrole. The mixture was cooled to 0°C by ice bath and TBAF (1M in THF, 1.68 mmol, 2.2 eq) was added slowly. After addition, the reaction was allowed to come back to room temperature and stirred for 12 h. The solvent was removed and the crude compound was purified by column chromatography (Silica, DCM:heptane = 1:1), giving pure compound.

Yield: 343 mg (70%) 2, 142.9, 140.5, 140.0, 136.1, 135.2, 135.0, 132.3, 131.3, 126.4, 125.5, 124.4, 123.7, 123.6, 121.7, 119.4, 115.5, 112.9, 105.8, 84.4, 81.4. UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 421 (130.4), 582 (21.9), 621 (17.7), 652 (11.3).

FTIR (KBr, cm -1 ): 2107 (CC). Nickel porphyrin 34 (5.85 g, 6.47 mmol, 1 eq) was stirred in THF (200 mL) and MeOH (200 mL), to which a solution of KOH (17.4 g, 310 mmol, 48 eq) in H2O (200 mL) was introduced.

This mixture was refluxed for 12 h. After cooling down to room temperature, THF and MeOH were evaporated. Additional water was added to the resulting water phase and the mixture was heated until the solid was fully dissolved, then the homogeneous solution was acidified with 1M HCl until no further precipitate was detected. The solid was collected by filtration, washed with water and dried in vacuum.

Yield: 5.68 g (91%)

1 H NMR (500 MHz, DMSO-d6) δ 13.27 (s, 4H), 8.71 (s, 8H), 8.29 (d, J = 8.0 Hz, 8H), 8.12 (d, J = 8.0 Hz, 8H).

Synthesis of platform precursors

Tetraphenylmethane (36) 23 The compound was synthesized according to the literature with a slight modification. 23 In a 500 mL round bottom flask, chlorotriphenylmethane (25.0 g, 89.7 mmol, 1 eq) and aniline (22.0 mL, 22.5 g, 232 mmol, 2.6 eq) were added. The mixture was stirred vigorously and slowly heated to 190°C. The mixture was stirred at 190°C for 1 h, until all residues became solid. After grinding all the solid into powder, a solution of aqueous HCl (2 M, 100 mL) and methanol (150 mL) were added to the purple powder and the reaction mixture was heated to 80°C for more than 2 h. After cooling, the resulting solid was filtered off, washed with water and methanol and dried under vacuum, giving pink powder.

The dry solid was then suspended in DMF (250 mL) and the mixture was cooled to -15°C.

Sulfuric acid (96%, 27.5 mL) and isoamyl nitrite (19.9 mL, 17.3 g, 148 mmol, 1.7 eq) were added slowly and the resulting suspension was stirred for 1 h. The reaction mixture was allowed to warm up to room temperature. Then hypophosphoric acid (50%, 45 mL) was added dropwise.

After the addition, the mixture was heated at 50°C until the evolution of gas has ceased. Then, the solid was filtered off and washed subsequently with DMF, water, and ethanol and the washing procedure was repeated twice. After drying under vacuum, the pure product was obtained.

Yield: 15.0 g (52%)

1 H NMR (500 MHz, CDCl3) δ 7. 22-7.09 (m, 20H).

13 C NMR (125 MHz, CDCl3) δ 146. 9, 131.3, 127.6, 126.0, 65.1.

Tetrakis(4-nitrophenyl)methane (37)

This compound was synthesized according to the literature with a slight modification. 24 In a round bottom flask, compound 36 (4.00 g, 12.5 mmol, 1 eq) was slowly added to fuming nitric acid (22 mL) at 0°C. Then, glacial acetic acid (13.6 mL) and acetic anhydride (7.6 mL) were added. The mixture was stirred for 5 h and then filtered to give yellow-brown solid which was further washed with water, then dried and recrystallized from THF to give pure compound.

Yield: 4.38 g (70%)

Tetrakis(4-aminophenyl)methane (38)

Compound 38 was synthesized according to the literature with a slight modification. 24 The Pd/C catalyst (500 mg, 5% palladium on carbon, 50% water) was activated by heating at 100°C and vacuum for 3 h. A solution of compound 37 (1.90 g, 3.80 mmol, 1 eq) in dry THF (100 mL)

was added to the Pd/C catalyst. The reaction mixture was purged with nitrogen followed by dihydrogen and stirred for 12 h. Pd/C powder was filtered over celite. The filtrate was dried to give white compound.

Yield: 1.47 g (91%)

1 H NMR (500 MHz, DMSO-d6) δ 6.67 (d, J = 8.5 Hz, 8H), 6.39 (d, J = 8.5 Hz, 8H), 4.84 (s, 8H).

Tetrakis(4-bromophenyl)methane (39)

Compound 39 was synthesized according to the literature with a slight modification. 23 To a round bottom flask containing bromine (30 mL, 93.4 g, 0.59 mol, 24 eq), tetraphenylmethane 36 (8.00 g, 25.0 mmol, 1 eq) was added in small portions under vigorous stirring at room temperature. After the addition was completed, the resulting solution was stirred for 20 min and then cooled to -78°C. At this temperature, ethanol (150 mL) was added slowly and the reaction mixture was allowed to warm to room temperature overnight. After, the precipitate was filtered off and washed subsequently with saturated aqueous NaHSO3 solution and water, dried under vacuum. The crude compound was recrystallized with CHCl3/EtOH to afford yellow crystals.

Yield: 13.5 g (85%)

1 H NMR (500 MHz, CDCl3) δ 7.39 (d, J = 8.5 Hz, 8H), 7.01 (d, J = 8.5 Hz, 8H).

13 C NMR (125 MHz, CDCl3) δ 144. 6, 132.5, 131.2, 121.0, 63.8.

Tetrakis(4-formylphenyl)methane (40)

Compound 40 was synthesized according to the literature with a slight modification. 25 A solution of compound 39 (8.00 g, 12.6 mmol, 1 eq) in dry THF (250 mL) was stirred at -78°C under nitrogen and treated dropwise with a solution of n-butyllithium (50.0 mL, 2.5 M in hexane, 125 mmol). The resulting mixture was kept at -78 °C for 1 h, and then DMF (20.2 mL, 250 mmol) was added dropwise. The mixture was stirred overnight while the temperature was allowed to rise to room temperature. To the solution was added 1.0 M aqueous HCl (100 mL), and solvents were partially removed by evaporation under reduced pressure. The remaining aqueous concentrate was extracted with ethyl acetate, and the combined organic extracts were washed with water and brine, dried over MgSO4, and filtered. Solvents were removed by evaporation under reduced pressure, and the residue purified through column chromatography (Silica, toluene:acetone = 95:5), giving colorless compound.

Yield: 1.5 g (28%)

1 H NMR (500 MHz, CDCl3) δ 10.02 (s, 4H), 7.84 (d, J = 8.5 Hz, 8H), 7.43 (d, J = 8.5 Hz, 8H).

1,3,5,7-Tetrakisphenyladamantane (41)

The compound was synthesized according to the literature with a slight modification. 23 1-Bromoadamantane (14.0 g, 65.1 mmol, 1 eq) was dissolved in benzene (120 mL) under an argon atmosphere. t-Butylbromide (14.7 mL, 130 mmol, 2 eq) and aluminum chloride (0.75 g, 5.60 mmol, 0.1 eq) were added to the solution, which was then refluxed overnight. The reaction mixture was cooled to room temperature and the formed precipitate was filtered off and washed with chloroform, water, and again chloroform. The product was dried under reduced pressure overnight.

Yield: 18.0 g (64%)

1 H NMR (500 MHz, DMSO-d6) Insoluble in common organic solvents 1,3,5,7-Tetrakis(4-iodophenyl)adamantane (42)

Compound 42 was synthesized according to the literature with a slight modification. 23 Iodine (2.36 g, 9.06 mmol, 2 eq) was added to a suspension of 1,3,5,7-tetraphenyladamantane 41 (2.00 g, 4.54 mmol, 1 eq) in chloroform (50 mL) and the mixture was stirred until the iodine had dissolved. Then, (bis(trifluoroacetoxy)iodo)benzene (3.90 g, 9.06 mmol, 2 eq) was added and the suspension was stirred for 24 h at room temperature. The mixture was filtered to remove a purple solid. The organic layer was washed with saturated aqueous sodium bisulfite solution (5%, 50 mL), water (50 mL), and brine (50 mL), and dried over magnesium sulfate. The product was recrystallized in a chloroform/methanol mixture (9:1, v:v) to isolate colorless crystals of 1,3,5,7-tetrakis(4-iodophenyl)adamantane.

Yield: 1.9 g (44%)

1 H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 8.5 Hz, 8H), 7.18 (d, J = 8.5 Hz, 8H), 2.05 (s, 12H). Compound 48 was synthesized according to the literature with a slight modification. 30 Truxene 47 (1.83 g, 2.0 mmol, 1 eq) and anhydrous ethyl ether (80 mL) were added to a flask under nitrogen. The mixture was cooled to -78°C and n-BuLi (7.30 mL, 18.3 mmol, 2.4 M in hexane) was dropwise under nitrogen. After addition, the reaction was stirred for 30 min at -78°C then allowed to warm up to room temperature and stirred for 30 min.

COF-4

A Schlenk tube was charged with aldehyde corrole 16 (22.6 mg, 0.036 mmol, 2 eq) and platform

(10 mg, 0.018 mmol, 1 eq) in a mixed solution of n-BuOH (2 mL), mesitylene (1 mL) and 6 M aqueous acetic acid (0.2 mL). The mixture was sonicated for 10 min to completely solubilize the starting materials. Then the Schlenk tube was sealed and the mixture was flash frozen at 77 K (liquid N2 bath), followed by three freeze-pump-thaw cycles and sealed under vacuum. The reaction mixture was heated at 120 °C for 24 h to afford a dark precipitate which was isolated by centrifugation and washed by THF several times. The product was dried under vacuum for 24 hours to afford dark powder.

Yield: 22.2mg (68%).

FTIR (KBr, cm -1 ): 1616 (C=N imine bond).

Bourgogne

  (ICMUB, UMR 6302), team Polyamines, Porphyrines, Développements et Applications (P2DA).

Figure 7 .

 7 Figure 7. Isotherms adsorption of CO, N2 and O2 for 5,10,15-tris(2,6-dichlorophenyl)corrolato]cobalt at 298K. Adsorption isotherms of CO (blue circles), O2 (pink squares) and N2 (red triangles) for cobalt corrole recorded at 298 K. Solid lines represent the fitting curves using a triple-site Langmuir model for CO and a single one for O2

Figure 9 .

 9 Figure 9. Evolution of the covalent organic framework chemistry. 181

Figure 10 .

 10 Figure 10. A general strategy for the design and synthesis of weaving structures (COF-505). 184

Figure 11 .

 11 Figure 11. Topology diagrams representing a general basis for COF design and construction of (A) 2D COFs and (B) 3D COFs. 191

Figure 12 .

 12 Figure 12. Schematic representation of crystalline and amorphous covalent organic framework formation by reversible and irreversible reactions. 181

Figure 13 .

 13 Figure 13. Various linkages explored for the synthesis of COFs (part 1). 190

Figure 13 .

 13 Figure 13. Various linkages explored for the synthesis of COFs (part 2). 190

Figure 14 .

 14 Figure 14. (a) Self-condensation of BDBA to produce COF-1 (b) Co-condensation of BDBA and HHTP to synthesize COF-5. 164

Figure 16 .

 16 Figure 16. Synthesis of spiroborate linkage COFs. 224

  as hexanes, methanol, acetone, tetrahydrofuran, and N,N-dimethylformamide. The application of the Brunauer-Emmett-Teller (BET) model results in a surface area of SBET = 1360 m 2 g -1 ,

Figure 18 .

 18 Figure 18. Synthesis of COF-300. The single framework (space filling, C gray and pink, N green, H white) and the dia-c5 topology. 209

Figure 19 .

 19 Figure 19. (a) Construction of COF-LZU1 and Pd/COF-LZU1. (b) Proposed structure of COF-LZU1. (c, d) Proposed structure of Pd/COF-LZU1. All structures were simulated with a 2D eclipsed layered-sheet arrangement. C: blue, N: red, and brown spheres represent the incorporated Pd(OAc)2. H atoms are omitted for clarity. 130

Figure 20 .

 20 Figure 20. Synthesis of (a) Py-Azine COF, (b) LZU-22, (c) Nx-COF (x = 0, 1, 2, and 3), and (d) HEX-COF 1. 190

Figure 21 .Figure 22 .

 2122 Figure 21. Schematic representation of the β-ketoenamine COF formation via enol-keto tau-tomerization.Adapted with permission.240

Figure 24 .

 24 Figure24. Building units and extended structures of PPy-COF and TP-COF.139, 140

Figure 25 .

 25 Figure 25. Synthesis and structures of Pa-COF and Tb-COF. 279

Figure 26 .

 26 Figure 26. Synthesis and structures of TPAPC-COF (a) and CorMeO-COF (b).280, 281

Figure 28 .

 28 Figure 28. (a) Schematic representation of two synthetic routes for preparing POPs based on cobalt corrole (I) using a post-metalation way and (II) using a direct synthesis from the cobalt corrole complex. (b) selective sorption of cobalt-corrole based POP towards CO vs N2, O2 and CO2. 302

Figure 30 .

 30 Figure 30. Prototypical examples of the inorganic building blocks and organic ligands, often used for the construction of MOFs. 323

Figure 31 .

 31 Figure 31. Crystal structure, structural components, and underlying network topology of Corrole-MOF-1 after removal of disorder: (a) tricarboxylic corrolic linker, H3TCPC; (b) D3d-symmetric 9-connected Zr6 cluster; (c) schematic representation of the (3,9)-connected net for Corrole-MOF-1 framework; (d) View of Corrole-MOF-1 along the c axes, with uniform 1D open channels. 324

Scheme 4

 4 Scheme 4 Synthetic routes of 5-[4-(5,5-Dimethyl-1,3-dioxan-2-yl)phenyl]dipyrromethane.

Scheme 5 .

 5 Scheme 5. Dipyrromethane synthesis catalyzed by MgBr2.

Figure 1 . 1 H

 11 Figure 1. 1 H NMR (500MHz) of mixture compounds from Scheme 1 in DMSO-d6.

Figure 2 .

 2 Figure 2. Mass spectrum of corroles 13.

  Scheme 8. Synthetic routes of bis-NH2-corrole.

Figure 3 . 1 H

 31 Figure 3. 1 H NMR (500 MHz) spectrum of corrole 15 and 16 in DMSO-d6 after addition of 50 L of hydrazine.

Scheme 15 .

 15 Scheme 15. Synthesis of 5,10,15-Tris(p-carboxymethylphenyl)corrole according two methods: a) one pot synthesis from aldehyde and pyrrole; b) synthesis from dipyrromethane and aldehyde.

Scheme 17 .

 17 Scheme 17. Synthesis of 5,10,15-tris(4-(benzyloxycarbonyl)phenyl)corrole.

Figure 4 . 1 H

 41 Figure 4. 1 H NMR (500 MHz)spectrum of corrole 20 in CD3OD after addition of 50 L of hydrazine.

Figure 5 .

 5 Figure 5. 13 C NMR (125 MHz) spectrum of corrole 20 in CD3OD after addition of 50 L of hydrazine.

Scheme 22 .

 22 Scheme 22. Synthesis of corrole 25.

of 5 ,

 5 Scheme 23. Synthesis of 5,15-diphenyl-10-(4-carboxyphenyl)corrole cobalt complex.

Scheme 24 .

 24 Scheme 24. Synthesis of 5,15-di(4-carboxyphenyl)-10-(4-trifluoromethyl)corrole.

Scheme 27 .

 27 Scheme 27. Synthesis of 5,15-di(4-ethynylphenyl)-10-(4-trifluoromethyl)corrole.

Scheme 1 .

 1 Scheme 1. Structures of A3 corrole and trans A2B corrole.

Scheme 6 .

 6 Scheme 6. Synthetic route to obtain 3D-COF-CorCo.

Scheme 8 .

 8 Scheme 8. Synthetic route to obtain 2D-COF-CorCo.

Figure 2 . 1 H

 21 Figure 2. 1 H NMR spectrum of 2D-COF-Cor decomposed by DCl.

Figure 3 . 1 H

 31 Figure 3. 1 H NMR spectrum of 3D-COF-Cor decomposed by DCl.

Figure 4 .

 4 Figure 4. FTIR spectra of 1,3,5-triformylbenzene, corrole-NH2 16 and 2D-COF-Cor.

Figure 5 .

 5 Figure 5. FT-IR spectra of tetrakis(4-formylphenyl)methane, corrole-NH2 16 and 3D-COF-Cor.

Figure 6 .

 6 Figure 6. FTIR spectra of 2D-COF-Cor, 2D-COF-CorCo-DMSO and 2D-COF-CorCo-NH3.

Figure 7 .

 7 Figure 7. FT-IR spectra of 3D-COF-Cor, 3D-COF-CorCo-DMSO and 3D-COF-CorCo-NH3.

Figure 8 .

 8 Figure 8. FT-IR spectra of NH3 release under vacuum from 2D-COF-CorCo-NH3 (a) and 3D-COF-CorCo-NH3 (b).

Figure 9 .

 9 Figure 9. Experimental PXRD patterns of 3D-COF-Cor.

Figure 10 .

 10 Figure 10. a. PXRD patterns of 2D-COF-Cor with the experimental in red, Pawley refined in black, difference between experimental and refined data in green, and simulated AA and AB stacking respectively in orange and blue. Space-filling models of the 2D-COF-Cor in b and c. AA stacking from top and side views respectively and d and e. AB stacking from top and side views respectively.

Figure 11 .

 11 Figure 11. a. Top view and b. side view of the optimized 2D-COF-Cor in the staggered AA stacking mode shown as space-filling model, indicating the pore aperture and stacking distance.

Figure 12 .

 12 Figure 12. Experimental PXRD patterns of 2D-COF-Cor and 2D-COF-CorCo.

Figure 13 .Figure 14 .

 1314 Figure 13. SEM images of COFs: a. 2D-COF-Cor, b. 3D-COF-Cor, c. 2D-COF-CorCo-DMSO, d. 3D-COF-CorCo-DMSO.

Figure 15 .

 15 Figure 15. Extracted points for EDS analysis of 3D-COF-CorCo-DMSO.

Figure 16 .

 16 Figure 16. Extracted points for EDS analysis of 2D-COF-CorCo-DMSO.

Figure 17 .

 17 Figure 17. Thermogravimetric analysis recorded for 2D-COF-Co, 2D-COF-CorCo, 3D-COF-Cor, and 3D-COF-CorCo under N2/O2 gas flow.

Figure 18 .

 18 Figure 18. a. N2 adsorption (closed symbols) and desorption (open symbols) isotherms recorded at 77 K for 2D-COF-Cor (blue square), 2D-COF-CorCo (green square), 2D-COF-CorCo after CO cycles (brown square). b. The respective pore size distribution curves of 2D-COF-Cor and 2D-COF-CorCo calculated using the NLDFT method.

Figure 19 .

 19 Figure 19. a. N2 adsorption (closed symbols) and desorption (open symbols) isotherms recorded at 77 K for 3D-COF-Cor (blue square), 3D-COF-CorCo (green square), 3D-COF-CorCo after CO cycles (brown square). b. The respective pore size distribution curves of 3D-COF-Cor and 3D-COF-CorCo calculated using the NLDFT method.

Figure 20 .

 20 Figure 20. N2 adsorption (closed symbols) and desorption (open symbols) isotherms recorded at 77 K for 3D-COF-Cor (a) and 2D-COF-Cor (b), before (red curve) and after one month (blue curve).

Figure 22 .

 22 Figure 22. CO adsorption isotherms for 2D-COF-CorCo recorded at 298 K for four successive cycles (1 st cycle: blue symbols; 2 nd cycle: red symbols; 3 rd cycle: green symbols; 4 th cycle: orange symbols). The sample was degassed at 80 °C during 3 h between each adsorption measurement.

Figure 23 .

 23 Figure 23. CO adsorption isotherms for 3D-COF-CorCo recorded at 298 K for four successive cycles (1 st cycle: blue symbols; 2 nd cycle: red symbols; 3 rd cycle: green symbols). The sample was degassed at 80 °C during 3 h between each adsorption measurement.

Figure 24 .

 24 Figure 24. FTIR monitoring of the adsorption/desorption process recorded for 2D-COF-CorCo: a. activated 2D-COF-CorCo and treated with CO for 1 h, b. during desorption under vacuum (1 min to 90 h).

Figure 25 .

 25 Figure 25. FTIR monitoring of the second adsorption/desorption process recorded for 2D-COF-CorCo.

Figure 26 .

 26 Figure 26. Intensity changes of FT-IR spectrum at 2044 cm -1 of 2D-COF-CorCo during desorption.

Figure 27 .

 27 Figure 27. FTIR monitoring of the adsorption/desorption process recorded for 3D-COF-CorCo: a. activated 2D-COF-CorCo and treated with CO for 1 h, b. during desorption under vacuum (1 min to 36 h).

Figure 28 .

 28 Figure 28. FTIR monitoring of the second adsorption/desorption process recorded for 3D-COF-CorCo.

Figure 29 .

 29 Figure 29. Intensity changes of FT-IR spectrum at 2044 cm -1 of 3D-COF-CorCo during desorption.

3. 3 . 4 . 2

 342 Scheme 11. Synthesis of COF-3.

Figure 30 .

 30 Figure 30. Structure simulation photo of truxene from front (left) and side (right).

1 H

 1 NMR (500 MHz, CDCl3) δ 10.03 (s, 1H), 7.89 (d, J = 8.5 Hz, 2H), 7.68 (d, J = 8.5 Hz, 2H), 5.45 (s, 1H), 3.80 (d, J = 11.0 Hz, 2H), 3.67(d, J = 11.0 Hz, 2H), 1.29 (s, 3H), 0.82 (s, 3H)

  (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 6.65 (m, 2H), 5.93 (m, 2H), 5.69 (m, 2H), 5.53 (s, 1H).

1 H

 1 NMR (500 MHz, DMSO-d6) δ 10.57 (s, 2H), 7.46 (d, J = 8.5 Hz, 2H), 7.10 (d, J = 8.5 Hz, 2H), 6.61 (m, 2H), 5.89 (m, 2H), 5.64 (m, 2H), 5.34 (s, 1H).

1 H

 1 NMR (400 MHz, DMSO-d6) δ 10.57 (s, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 6.61 (m, 2H), 5.89 (m, 2H), 5.63 (m, 2H), 5.37 (s, 1H), 0.22 (s, 9H).

  -di(4-(5,5-dimethyl-1,3-dioxacyclohex-2-yl)phenyl)-10(4trifluoromethyl)corrole was based on the general procedure A. The 13 is not described. For the reaction, dipyrromethane 5 (3.36 g, 10.0 mmol, 1 eq) and 4-trifluoromethylbenzaldehyde (871 mg, 5.0 mmol, 0.5 eq) were used. The collected residue after purification gives a mixture of targeted corrole 13 and sides products (corroles partially and/or totally deprotected). The mixture (212 mg) was directly used for next step.

(

  20 mL) and TFA(20 mL) under argon. The mixture was heated at 70°C for 2 h. The reaction was monitored by mass spectrometry. After cooling, the mixture was diluted by H2O, extracted with DCM. The organic layer was washed by NaHCO3 solution and dried by Na2SO4. The crude compound was purified by column chromatography with DCM as eluent, further recrystallized from THF/heptane, giving purple powder.Yield: 183 mg (5.6%) (calculated from 4-trifluoromethylbenzaldehyde)1 H NMR (500 MHz, DMSO-d6, 10 L Hydrazine, imine form was observed) δ 8.92 (d, J = 4.0 Hz, 2H), 8.67(d, J = 4.5 Hz, 2H), 8.52 (d, J = 4.0 Hz, 2H), 8.31 (d, J = 8.0 Hz, 2H), 8.26 (d, J = 4.5 Hz, 2H), 8.22 (d, J = 8.0 Hz, 4H), 8.06 (d, J = 8.5 Hz, 2H), 8.00 (s, 2H), 7.89 (d, J = 8.0 Hz, 4H).

13 C

 13 NMR (125 MHz, DMSO-d6, 10 L Hydrazine, imine form was observed) δ 164.

19 F

 19 NMR (470 MHz, DMSO-d6, 10 L Hydrazine) δ -60.15 (s, 3F). MS (MALDI-TOF): m/z = 651.062 [M+H] +. , 651.201 calcd for C40H26F3N4O2. HR-MS (ESI): m/z = 651.2002 [M+H] + , 651.2002 calcd for C40H26F3N4O2.

  Reduction of nitrocorrole 15 was carried out via a small modification of the procedure reported by Gros et al.15 266 mg of Pd/C (10%) was activated through heating and vacuum. After cooling, a solution of corrole 15 (1.03 g, 1.5 mmol, 1 eq) in dry THF (250 mL) was added to the former flask under argon and dry triethylamine (900 L) was followed. The flask was charged with dihydrogen to remove the argon and fill the flask. The mixture was stirred under dihydrogen for 12 h and reaction was stopped until all nitrocorrole was reduced to aminocorrole 16. The mixture was filtered on Celite and evaporated to remove solvent. The crude compound was purified on flash chromatography (Silica, DCM/TEA = 100:1), giving purple solid. Corrole 16 was kept under argon atmosphere and stored in the fridge. Yield: 0.80 g (89%) 1 H NMR (500 MHz, DMSO-d6, 10 L Hydrazine) δ 8.78 (d, J = 4.0 Hz, 2H), 8.59 (d, J = 4.5 Hz, 2H), 8.41 (d, J = 4.0 Hz, 2H), 8.25 (d, J = 8.0 Hz, 2H), 8.14 (d, J = 4.5 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.88 (d, J = 8.0 Hz, 4H), 6.99 (d, J = 8.0 Hz, 4H).13 C NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 149.

  ): m/z = 624.21 [M] +. , 624.22 calcd for C38H27F3N6. HR-MS (ESI): m/z = 625.2320 [M+H] + , 625.2322 calcd for C38H28F3N6.

Yield: 1

 1 Pd/C (10%) was activated through heating under vacuum. After cooling, a solution of corrole 18 (1.60 g, 1.72 mmol) in a mixture of dry THF (125 mL) and MeOH (125 mL) was added to the former flask under argon. The flask was charged with dihydrogen to remove the argon and fill the flask. The mixture was stirred under dihydrogen for 2 h and reaction was monitored by mass spectrum. The mixture was filtered on Celite and evaporated to remove solvent. The crude compound was collected and recrystallized from THF/MeOH/heptane, m/z 659.20 M+H + , 659.19 calcd for C40H27N4O6. HR-MS (ESI): m/z 659.1918 M+H + , 659.1925 calcd for C40H27N4O6.

1 H

 1 NMR (500 MHz, CDCl3 , 10 L Hydrazine) δ 8.88 (d, J = 4.0 Hz, 2H), 8.84 (d, J = 5.0 Hz, 2H), 8.52 (d, J = 4.0 Hz, 2H), 8.46 (d, J = 5.0 Hz, 2H), 8.40 (d, J = 8.0 Hz, 2H), 8.33-8.32 (m, 4H), 8.23 (d, J = 8.5 Hz, 2H), 7.78 (t, J = 7.5 Hz, 4H), 7.64 (t, J = 7.5 Hz, 2H), 4.07 (s, 3H).13 C NMR (125 MHz, CDCl3, 10 L Hydrazine) δ 167.

1 H

 1 NMR (500 MHz, DMSO-d6, 10 L Hydrazine) δ 8.91 (d, J = 4.0 Hz, 2H), 8.62 (d, J = 4.5 Hz, 2H), 8.48 (d, J = 4.0 Hz, 2H), 8.31 (d, J = 4.5 Hz, 2H), 8.27 (d, J = 8.0 Hz, 4H), 8.25 (d, J = 8.0 Hz, 2H), 8.05 (d, J = 8.0 Hz, 2H), 7.79 (t, J = 7.5 Hz, 4H), 7.64 (t, J = 7.5 Hz, 2H).13 C NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 171.

  -TOF): m/z = 570.86 [M] +. , 570.21 calcd for C38H26N4O2.HR-MS (ESI):m/z = 571.2129[M+H] + , 571.2129 calcd for C38H27N4O2.UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 3018 (broad peak, OH carboxyl), 1673 (C=O carboxyl).Dimethylsulfoxide 5,15-diphenyl-10-(4-carboxylphenyl)corrolato-cobalt(III)(23) In a round bottom flask, a solution of corrole 22 (200 mg, 0.35 mmol, 1 eq) and cobalt acetylacetonate (95.1 mg, 0.37 mmol, 1.05 eq) in dimethylsulfoxide (100 mL) was degassed with argon. The mixture was heated at 80°C for 40 min under argon and the reaction was monitored by mass spectrometry. After cooling, the mixture was poured into ice water and HCl solution (1M) was added to let the product precipitate, followed by addition of saturated NaCl solution. The corrole complex was collected by centrifugation and washed with water 2 times, then dried under vacuum, to give pure compound. Yield: 215 mg (87%) 1 H NMR (500 MHz, MeOD-d4, 10 L Hydrazine) δ 9.11 (d, J = 4.0 Hz, 2H), 8.94 (d, J = 4.5 Hz, 2H), 8.78 (d, J = 4.5 Hz, 2H), 8.70 (d, J = 4.0 Hz, 2H), 8.35 (d, J = 8.0 Hz, 2H), 8.26 (d, J = 8.0 Hz, 4H), 8.23 (d, J = 8.0 Hz, 2H), 7.79 (t, J = 8.0 Hz, 4H), 7.72 (t, J = 8.0 Hz, 2H), 2.67 (s, 6H), -3.49 (s, 4H). MS (MALDI-TOF): m/z = 626.19 [M-DMSO] + , 626.11 calcd for C38H23CoN4O2. HR-MS (ESI): m/z = 626.1146 [M-DMSO] + , 626.1148 calcd for C38H23CoN4O2.

1 H

 1 NMR (500 MHz, CDCl3) δ 9.10 (d, J = 4.0 Hz, 2H), 8.74 (d, J = 4.5 Hz, 2H), 8.66 (d, J = 4.5 Hz, 2H), 8.58 (d, J = 4.0 Hz, 2H), 8.37 (d, J = 8.0 Hz, 2H), 8.25 (d, J = 8.0 Hz, 2H), 4.02 (s, 3H).

19 F

 19 NMR (470 MHz, DMSO-d6) δ -137.83 (m, 4F), -152.63 (m, 2F), -161.66 (m, 4F).MS (MALDI-TOF):m/z = 765.24[M+H] + , 765.13 calcd for C39H19F10N4O2.HR-MS (ESI):m/z = 765.1342[M+H] + , 765.1343 calcd for C39H19F10N4O2.

1 H

 1 NMR (500 MHz, MeOD-d4) δ 9.06 (d, J = 4.0 Hz, 2H), 8.57 (d, J = 4.5 Hz, 2H), 8.54 (d, J = 4.5 Hz, 2H), 8.52 (d, J = 4.5 Hz, 2H) 8.28 (d, J = 8.0 Hz, 2H), 8.16 (d, J = 8.0 Hz, 2H).

19 F

 19 NMR (470 MHz, MeOD-d4) δ -140.34 (m, 4F), -159.04 (t, J = 20.0 Hz, 2F), -166.47 (m, 4F). MS (MALDI-TOF): m/z = 751.41 [M+H] + , 751.12 calcd for C38H17F10N4O2. HR-MS (ESI): m/z = 751.1185 [M+H] + , 751.1186 calcd for C38H17F10N4O2.

  -TOF): m/z = 721.79[M+H] + , 721.07 calcd for C39H25Cl4N4O2.HR-MS (ESI):m/z = 721.0739[M+H] + , 721.0732 calcd for C39H25Cl4N4O2.

19 Corrole

 19 27 was obtained according to general procedure C described above. For the reaction, corrole 26 (200 mg, 0.28 mmol, 1 eq) and NaOH (332 mg, 8.31 mmol, 30 eq) were used. The crude compound was collected and purified by column chromatography (Silica, DCM:MeOH = 100:5), giving purple solid. Yield: 195 mg (99%) 1 H NMR (500 MHz, DMSO-d6, 10 L Hydrazine) δ 8.84 (d, J = 4.0 Hz, 2H), 8.25 (d, J = 4.5 Hz, 2H), 8.20 (d, J = 8.0 Hz, 2H), 8.17 (d, J = 4.0 Hz, 2H), 8.15 (d, J = 4.0 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.86 (d, J = 8.5 Hz, 4H), 7.74 (m, 2H).

  -TOF): m/z = 707.82[M+H] + , 707.05 calcd for C38H23Cl4N4O2.HR-MS (ESI):m/z = 707.0565[M+H] + , 707.0570 calcd for C38H23Cl4N4O2.UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1Corrole 29 was obtained according to general procedure C described above. For the reaction, corrole 28 (500 mg, 0.70 mmol, 1 eq) and NaOH (1.69 g, 42.0 mmol, 60 eq) were used. The crude compound was collected and purified by column chromatography (Silica, DCM:MeOH = 100:5), giving purple solid.Yield: 436 mg (91%) 1 H NMR (500 MHz, DMSO-d6, 10 L Hydrazine) δ 8.92 (d, J = 4.0 Hz, 2H), 8.66 (d, J = 4.5 Hz, 2H), 8.51 (d, J = 4.0 Hz, 2H), 8.31 (d, J = 8.0 Hz, 2H), 8.29 (d, J = 8.0 Hz, 4H), 8.26 (d, J = 8.0 Hz, 2H), 8.19 (d, J = 8.0 Hz, 4H), 8.06 (d, J = 8.0 Hz, 2H).

13 C

 13 NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 149.

19 F

 19 NMR (470 MHz, DMSO-d6, 10 L Hydrazine) δ -60.16 (s, 3F).MS (MALDI-TOF): m/z = 683.29 [M+H] + , 683.19 calcd for C40H26F3N4O4. HR-MS (ESI): m/z = 683.1901 [M+H] + , 683.1901 calcd for C40H26F3N4O4.

  -TOF): m/z = 786.28 [M] +. , 786.28 calcd for C48H41F3N4Si2. HR-MS (ESI): m/z = 786.2809 [M] +. , 786.2816 calcd for C48H41F3N4Si2.

1 H

 1 NMR (500 MHz, DMSO-d6, 10 L Hydrazine) δ 8.95 (d, J = 4.0 Hz, 2H), 8.64 (d, J = 4.5 Hz, 2H), 8.51 (d, J = 4.0 Hz, 2H), 8.29 (d, J = 8.0 Hz, 2H), 8.27 (d, J = 4.5 Hz, 2H), 8.25 (d, J = 8.0 Hz, 4H), 8.05 (d, J = 8.0 Hz, 2H), 7.88 (d, J = 8.0 Hz, 4H), 4.33 (s, 2H).13 C NMR (125 MHz, DMSO-d6, 10 L Hydrazine) δ 149.

19 F

 19 NMR (470 MHz, DMSO-d6, 10 L Hydrazine) δ -60.0 (s, 3F). MS (MALDI-TOF): m/z = 642.09 [M] +. , 642.20 calcd for C42H25F3N4. HR-MS (ESI): m/z = 643.2091 [M+H] + , 643.2104 calcd for C42H26F3N4.

1 H

 1 NMR (500 MHz, CDCl3) δ 8.23 (d, J = 9.0 Hz, 8H), 7.41 (d, J = 9.0 Hz, 8H).

  The reaction was cooled to -78 °C again and DMF(1.42 g, 19.5 mmol) was slowly added to the flask. The reaction was stirred overnight and quenched with aqueous hydrochloric acid (2 M, 100 mL). The organic layer was washed with aqueous sodium chloride solution (20 mL × 3) and dried over sodium sulfate. The solvent was evaporated under vacuum and the solid was purified by column chromatography (Silica, DCM:heptane = 6:4), giving yellow powder.Yield: 1.23 g (81%)1 H NMR (500 MHz, CDCl3) δ 10.16 (s, 3H), 8.57(d, J = 8.0 Hz, 3H), 8.03 (d, J = 1.5 Hz, 3H), 7.79 (dd, J = 8.0 Hz, J = 1.5 Hz, 3H), 3.03-2.94 (m, 6H), 2.29-2.19 (m, 6H), 1.00-0.80 (m, 12H),0.58-0.36 (m, 30H).

7 CO concentration COHb level Signs and symptoms

	35 ppm	<10%	Headache and dizziness within 6 to 8 h of constant exposure
	100 ppm	>10%	Slight headache in 2 to 3 h
	200 ppm	20%	Slight headache within 2 to 3 h; loss of judgment
	400 ppm	25%	Frontal headache within 1 to 2 h
	800 ppm	30%	Dizziness, nausea, convulsions within 45 min; insensible within 2 h
	1600 ppm	40%	Headache, tachycardia, dizziness, nausea within 20 min; death in less
			than 2 h
	3200 ppm	50%	Headache, dizziness, nausea in 5 to10 min; death within 30 min
	6400 ppm	60%	Headache and dizziness in 1 to 2 min; convulsions, respiratory arrest,
			and death in less than 20 min
	12800 ppm	>70%	Death in less than 3 min

Table 2

 2

. Periodic table of metallocorroles. The shaded elements indicate specific corroles that have so far been electrochemically examined.

102

  enantioseparation,143, 144 drug delivery and release, 145 iodine adsorption, 146 detection and removal of pollutants/contaminants from water/other liquids,147, 148

  286, 287 et al. It is very easy to characterize the order of COFs structures thanks to the dynamic covalent bonding. In contrast, amorphous POPs do not form regular structures and pores. They are obtained according to an irreversible reaction. Covalent bonds are robust and MOFs generally have high stability. This advantage makes them popular on catalyst application because of the high recyclability and stability.145 Up to date, a great number of amorphous POPs have been developed mainly by cross-coupling reactions such as Sonogashira,288, 289 Suzuki,290, 291 Heck, 292, 293 Click.294, 295 Similar to MOFs and COFs, porous organic polymers (POPs) are well known for their unique physiochemical properties such as structural diversity, 162 good hydrothermal stability, 296 large surface area, 297 low density.298 POPs are promising materials for a wide range of applications including gas storage/separation, 299 optoelectronics, 300 catalysis, 271 sensors, 297 drug delivery 301 …

Figure 27. Schematic representation of crystalline COFs and amorphous POPs.

181

  Tetrahedron 1994, 50(39), 11427-11440. 77. Nardis, S.; Mandoj, F.; Stefanelli, M.; Paolesse, R., Metal complexes of corrole. Coord. Experimental and Theoretical Investigations of the Existence of Cu II , Cu III , and Cu IV in Copper Corrolato Complexes. Angew. Chem. Int. Ed. 2015, 54 (46), 13769-13774. Chem. Rev. 2017, 117 (4), 3377-3419. 103. Zhou, Y.; Xing, Y.-F.; Wen, J.; Ma, H.-B.; Wang, F.-B.; Xia, X.-H., Axial Ligands Tailoring the ORR Activity of Cobalt Porphyrin.Sci. Bull. 2019, 64 (16), 1158-1166.

	Chapter 2: Synthesis of precursors for porous materials
	Chem. Rev. 2017, 117 (4), 2711-2729.
	91. Lemon, C. M.; Marletta, M. A., Corrole-Substituted Fluorescent Heme Proteins. Inorg.
	Chem. 2021, 60 (4), 2716-2729.
	Chem. Rev. 2019, 388, 360-405. 92. Lopes, S. M. M.; Pineiro, M.; Pinho e Melo, T. M. V. D., Corroles and Hexaphyrins: 104. Kadish, K. M.; Shen, J.; Frémond, L.; Chen, P.; El Ojaimi, M.; Chkounda, M.; Gros, C.
	78. Mondal, S.; Naik, P. K.; Adha, J. K.; Kar, S., Synthesis, characterization, and reactivities Synthesis and Application in Cancer Photodynamic Therapy. Molecules 2020, 25 (15), P.; Barbe, J.-M.; Ohkubo, K.; Fukuzumi, S.; Guilard, R., Clarification of the Oxidation
	of high valent metal-corrole (M = Cr, Mn, and Fe) complexes. Coord. Chem. Rev. 2019, 3450. State of Cobalt Corroles in Heterogeneous and Homogeneous Catalytic Reduction of
	400, 213043. 93. Sinha, W.; Sommer, M. G.; Deibel, N.; Ehret, F.; Bauer, M.; Sarkar, B.; Kar, S., Dioxygen. Inorg. Chem. 2008, 47 (15), 6726-6737.
	79. Alemayehu, A. B.; McCormick, L. J.; Vazquez-Lima, H.; Ghosh, A., Relativistic Effects 105. Kadish, K. M.; Smith, K. M.; Guiland, R.; Editors, The Porphyrin Handbook: Volume 16
	on a Metal-Metal Bond: Osmium Corrole Dimers. Inorg. Chem. 2019, 58 (4), 2798-2806. / Phthalocyanines: Spectroscopic and Electrochemical Characterization. Academic
	Press: 2003; 288.
	Chapter 2
	Synthesis of precursors for porous
	materials
	Synthesis, Characterization, and Electrochemistry of σ-Bonded Cobalt Corroles in High
	Control of clustering behavior in anionic cerium(iii) corrole complexes: from oligomers to Oxidation States. Inorg. Chem. 1996, 35 (19), 5577-5583.
	monomers. Dalton trans. 2016, 45 (46), 18653-18660. Materials Incorporating Functionalized Cobalt(III) Corroles for the Selective Detection 111. Shah, M. N.; Pathipati, S. R.; Mehmood, S.; Kahn, F. U.; Sohail, M.; Ullah, B.; Yang, Y.;
	87. Aviv, I.; Gross, Z., Corrole-based applications. Chem. Comm. 2007, (20), 1987-1999. of CO. Angew. Chem. Int. Ed. 2005, 44 (20), 3103-3106. Pan, X., Stable Cobalt Porphyirn Ometed Type Small Molecule Sensor for the Sensitive
	88. Liu, H.-Y.; Mahmood, M. H. R.; Qiu, S.-X.; Chang, C. K., Recent developments in 101. Barbe, J.-M.; Canard, G.; Brandès, S.; Jérôme, F.; Dubois, G.; Guilard, R., and Selective Detection of Ammonia Gas at Room Temperature. Adv. Mater. Technol.
	manganese corrole chemistry. Coord. Chem. Rev. 2013, 257 (7), 1306-1333. Metallocorroles as sensing components for gas sensors: remarkable affinity and 2021, 6 (9), 2100147.

80. Kumar, A.; Yadav, P.; Majdoub, M.; Saltsman, I.; Fridman, N.; Kumar, S.; Kumar, A.; Mahammed, A.; Gross, Z., Corroles: The Hitherto Elusive Parent Macrocycle and its Metal Complexes. Angew. Chem., Int. Ed. 2021, 60 (47), 25097-25103. 81. Di Natale, C.; Gros, C. P.; Paolesse, R., Corroles at work: a small macrocycle for great applications. Chem. Soc. Rev. 2022, 51 (4), 1277-1335. 82. Ueta, K.; Fukuda, M.; Kim, G.; Shimizu, S.; Tanaka, T.; Kim, D.; Osuka, A., The First Silicon(IV) Corrole Complexes: Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer. Chem. Eur. J. 2018, 24 (30), 7637-7646. 83. Pomarico, G.; Monti, D.; Bischetti, M.; Savoldelli, A.; Fronczek, F. R.; Smith, K. M.; Genovese, D.; Prodi, L.; Paolesse, R., Silicon(IV) Corroles. Chemistry 2018, 24 (33), 8438-8446. 84. Einrem, R. F.; Braband, H.; Fox, T.; Vazquez-Lima, H.; Alberto, R.; Ghosh, A., Synthesis and Molecular Structure of 99 Tc Corroles. Chem. Eur. J. 2016, 22 (52), 18747-18751. 85. Ziegler, J. A.; Buckley, H. L.; Arnold, J., Synthesis and reactivity of tantalum corrole complexes. Dalton trans. 2017, 46 (3), 780-785. 86. Armstrong, K. C.; Hohloch, S.; Lohrey, T. D.; Zarkesh, R. A.; Arnold, J.; Anstey, M. R., 89. Zhang, Y.; Wang, Q.; Wen, J.; Wang, X.; Mahmood, M. H.; Ji, L.; Liu, H., DNA Binding and Oxidative Cleavage by a Water-soluble Carboxyl Manganese(III) Corrole. Chinese J. Chem. 2013, 31 (10), 1321-1328. 90. Teo, R. D.; Hwang, J. Y.; Termini, J.; Gross, Z.; Gray, H. B., Fighting Cancer with Corroles. 94. Alemayehu, A. B.; McCormick, L. J.; Gagnon, K. J.; Borisov, S. M.; Ghosh, A. Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence. ACS Omega 2018, 3 (8). 9360-9368. 95. Yadav, O.; Varshney, A.; Kumar, A., Manganese(III) mediated synthesis of A2B Mn(III) corroles: A new general and green synthetic approach and characterization. Inorg. Chem. Comm. 2017, 86, 168-171.

96. Paolesse, R.; Nardis, S.; Monti, D.; Stefanelli, M.; Di Natale, C., Porphyrinoids for Chemical Sensor Applications. Chem. Rev. 2017, 117 (4), 2517-2583. 97. Brennan, B. J.; Lam, Y. C.; Kim, P. M.; Zhang, X.; Brudvig, G. W., Photoelectrochemical Cells Utilizing Tunable Corroles. ACS Appl. Mater. Interfaces 2015, 7 (29), 16124-16130. 98. Chen, T.-H.; Kwong, K. W.; Lee, N. F.; Ranburger, D.; Zhang, R., Highly efficient and chemoselective oxidation of sulfides catalyzed by iron(III) corroles with iodobenzene diacetate. Inorganica Chim. Acta 2016, 451, 65-72. 99. Barbe, J.-M.; Canard, G.; Brandès, S.; Guilard, R., Selective Chemisorption of Carbon Monoxide by Organic-Inorganic Hybrid Materials Incorporating Cobalt(III) Corroles as Sensing Components. Chem. Eur. J. 2007, 13 (7), 2118-2129. 100. Barbe, J.-M.; Canard, G.; Brandès, S.; Guilard, R., Organic-Inorganic Hybrid Sol-Gel selectivity of cobalt(iii) corroles for CO vs. O2 and N2. Dalton Trans. 2004, (8), 1208-1214. 102. Fang, Y.; Ou, Z.; Kadish, K. M., Electrochemistry of Corroles in Nonaqueous Media. 106. Ganguly, S.; Conradie, J.; Bendix, J.; Gagnon, K. J.; McCormick, L. J.; Ghosh, A., Electronic Structure of Cobalt-Corrole-Pyridine Complexes: Noninnocent Five-Coordinate Co(II) Corrole-Radical States. J. Phys. Chem. A 2017, 121 (50), 9589-9598. 107. Simkhovich, L.; Galili, N.; Saltsman, I.; Goldberg, I.; Gross, Z., Coordination Chemistry of the Novel 5,10,15-Tris(pentafluorophenyl)corrole: Synthesis, Spectroscopy, and Structural Characterization of Its Cobalt(III), Rhodium(III), and Iron(IV) Complexes. Inorg. Chem. 2000, 39 (13), 2704-2705. 108. Dong, S. S.; Nielsen, R. J.; Palmer, J. H.; Gray, H. B.; Gross, Z.; Dasgupta, S.; Goddard, W. A., Electronic Structures of Group 9 Metallocorroles with Axial Ammines. Inorg. Chem. 2011, 50 (3), 764-770. 109. Maiti, N.; Lee, J.; Kwon, S. J.; Kwak, J.; Do, Y.; Churchill, D. G., Synthetic, crystallographic and electrochemical studies of thienyl-substituted corrole complexes of copper and cobalt. Polyhedron 2006, 25 (7), 1519-1530. 110. Will, S.; Lex, J.; Vogel, E.; Adamian, V. A.; Van Caemelbecke, E.; Kadish, K. M., 112. Ganguly, S.; Renz, D.; Giles, L. J.; Gagnon, K. J.; McCormick, L. J.; Conradie, J.; Sarangi, R.; Ghosh, A., Cobalt-and Rhodium-Corrole-Triphenylphosphine Complexes

Table 1 .

 1 Synthetic conditions for COFs based on porphyrins.

	COFs	Porphyrin linker	Type	Synthetic condition	ref
	3D-TPP	5,15-bis(4-formylphenyl)-10,20-diphenylporphyrin	3D	120°C, 72 h 1,4-Dioxane / 3 M AcOH (35 :2 v/v),	33
	3D-Por-COF	5,10,15,20-tetrakis(4-benzaldehyde)porphyrin	3D	v/v/v), 120°C, 7d o-DCB / n-BuOH /6 M AcOH (9:1:1	9
	2D-PdPor-COF	[5,10,15,20-tetrakis(4-benzaldehyde)-porphyrin]palladium	2D	v/v/v), 120°C, 72 h o-DCB / n-BuOH / 3 M AcOH (5:5:1	32
	Por-C=N-COF	5,10,15,20-tetrakis(4-benzaldehyde)porphyrin	2D	v/v/v), 120°C, 72 h o-DCB / n-BuOH / 3 M AcOH (5:5:1	31
	PPOP-1	5,15-di(4-aminophenyl)-10,20-diphenylporphyrin	3D	v/v/v), 120°C, 72 h o-DCB / n-BuOH / 6 M AcOH (7:3:1	30
	CPF-1	5,15-di(4-aminophenyl)-10,20-diphenylporphyrin	2D	(15:15:1 v/v/v), 120°C, 72 h 1,4-dioxane / mesitylene/ 6 M AcOH	29
	PCOF-1	5, 10, 15, 20-tetra(4-aminophenyl)porphyrin	3D	(17:3:2 v/v/v), 120°C, 7 d o-DCB / mesitylene / 6 M AcOH	24
	TT-Por COF	5, 10, 15, 20-tetra(4-aminophenyl)porphyrin	2D	(5:15:2 v/v/v), 120°C, 72 h o-DCB / benzyl alcohol / 6 M AcOH	28
	From Table 1, we can see that COFs based on porphyrin (with aldehyde or amino functions)
	are synthesized under catalysis of aqueous acetic acid (3 M or 6 M) at 120°C for a long reaction
	time. Also, the solvents used for the synthesis are high boiling point solvents e.g. like 1,4-
	Dioxane, o-DCB, n-BuOH, mesitylene. It should be noted that due to the use of aqueous acetic

Table 2 .

 2 Synthetic conditions for COF-1 synthesisFirstly, we tried small scale tests for the synthesis. Experiments 1 and 2 were carried out with 6 M aqueous acetic acid at 80°C and the solvents were 1,4-dioxane and a mixture of n-was collected by centrifugation or filtration and washed with an appropriate solvent at room temperature. The residue was dried under vacuum and kept under nitrogen or argon in the dark. The COFs n°1 and n°2 were first characterized by Powder X-ray Diffraction but, to our surprise, they do not show any crystallinity. Both COFs have been obtained in quite low

			Solvent		Catalyst
		1,4-Dioxane	THF	n-BuOH	o-DCB	6M AcOH	Crystallinity	SBET (m 2 /g)
	1	1 mL	-	-	-	0.1 mL	Amorphous	-
	2	-	-	0.1 mL	0.9 mL	0.1 mL	Amorphous	-
	3	-	1 mL	-	-	0.1 mL	-	-
	BuOH / o-DCB. The reported COF based porphyrin were synthesized at 120°C, but we first
	tried 80°C here considering that corrole is generally less stable than porphyrin. A mixture of
	corrole 14 (10.0 mg, 0.016 mmol, 2 eq) and platform 38 (3.00 mg, 0.008 mmol, 1 eq), 6 M

aqueous acetic acid, and solvents were placed in a Schlenk tube of suitable volume. The mixture was sonicated for a short period, degassed via freeze-pump-thaw cycles, sealed with a glass stopper and kept at 80°C for 24 h. The tube was then cooled at room temperature, and the precipitate

Table 6 .

 6 EDS analysis of 3D-COF-CorCo-DMSO in atom %.

		C	O	F	S	Co
	point 1	70.14	20.94	4.73	0.45	0.93
	point 2	73.33	18.55	4.88	0.41	0.91
	point 3	74.81	16.9	4.94	0.41	1.01
	point 4	70.07	17.36	6.3	0.72	1.31
	point 5	66.94	21.49	9.09	0.85	1.64
	point 6	68.93	18.67	6.55	0.68	1.23
	point 7	69.08	18.83	6.32	0.63	1.26

Table 7 .

 7 Metalation ratio calculation from EDS for 3D-COF-CorCo-DMSO.

		Co/F	Metalation
		(Atomic ratio)	(Co/F EDS ÷ theo)
	Point 1	0.20	0.60
	point 2	0.19	0.58
	point 3	0.20	0.60
	point 4	0.21	0.64
	point 5	0.18	0.56
	point 6	0.19	0.58
	Point 7	0.20	0.60
	average	0.19	0.58

Table 8 .

 8

		C	O	F	S	Co
	point 1	80.78	6.75	6.72	2.32	3.44
	point 2	77.39	10.63	9.35	1.15	1.5
	point 3	79.62	8.69	8.57	1.35	1.78
	point 4	79.4	8.68	8.5	1.48	1.94
	point 5	78.96	9.22	8.4	1.47	1.94
	point 6	79.18	9.21	8.34	1.37	1.89

EDS analysis of 2D-COF-CorCo-DMSO in atom %.

Table 9 .

 9 Metalation ratio calculation from EDS for 2D-COF-CorCo-DMSO.

		Co/F	Metalation
		(Atomic ratio)	(Co/F EDS ÷ theo)
	point 1	0.51	1.54 *
	point 2	0.16	0.48 *
	point 3	0.21	0.64
	point 4	0.23	0.70
	point 5	0.23	0.70
	point 6	0.23	0.70
	average	0.22	0.67

Table 7 .

 7 Thermogravimetric data for the 3D-COF-CorCo.

	Material	mexp(%)	%CoOexp(calcd) a	Co metalation ratio
	3D-COF-CorCo	7.3	7.9	92%

Table 8 .

 8 Optimization of synthetic conditions for COF-2.

  ). Inspired by recently reported corrole-based MOF based, we will try to reproduce this MOF-corrole and metalate it with cobalt to test it ability for CO detection. Also reported in chapter 2 was the synthesis of mono-COOH corroles. Since it has already been shown that MOF PCN-222 contains free zirconium sites, it is anticipated that mono-COOH corroles could be used to functionalize PCN-222. Moreover, the high porosity and stability of PCN-222 make it a suitable carrier to hold corroles. For corrole-based POPs based, we synthesized bis-alkyne corrole and 1,3,5,7-Tetrakis(4-iodophenyl)adamantane, and following the early reported POP-Cor by our group, we can try similar reaction conditions to synthesize new POP based on a more rigid adamantane platform.

-Diphenyl-10-(4-carboxylphenyl)corrole (22) 17

	5,15
	HR-MS (ESI): m/z = 585.2286 [M+H] + , 585.2285 calcd for C39H29N4O2.
	UV-vis (DCM): max (nm) (  10 -3 L mol -1 cm -1 ) 415 (113.6), 434 (86.3), 576 (17.7), 614
	(13.2), 650 (8.6).
	FTIR (KBr, cm -1 ): 1704 (C=O ester),

-TOF): m/z = 584.834 [M] +. , 584.22 calcd for C39H28N4O2.

* Point 1 and point 2 were not taken into account.

F NMR (470 MHz, DMSO-d6, 10 L Hydrazine) δ -60.19 (s, 3F).

H NMR spectrum of COF-1 decomposed by DCl in DMSO-d6.

Acknowledgments

This thesis work was carried out at the Institut de Chimie Moléculaire de l'Université de

For the next step, the trimethylsilylacetylene functions were deprotected with TBAF (Scheme 27). The resulted di-alkyne corrole was purified by flash chromatography, giving a high yield of 95%. In order to raise the crystallinity and BET surface area, optimization of synthetic conditions for the 3D-COFs-Cor was required. To obtain the best synthetic condition, we have tried several experiments carried in different solvents (Table 4). These experiments were launched with the same quantity of starting materials: corrole 16 (28.9 mg, 0.046 mmol, 2 eq) and platform 40 (10.0 mg, 0.023 mmol, 1 eq). All the reactions were catalyzed with 6M acetic acid at 120°C during 24h and resulted materials were characterized with PXRD and BET measurements. Inside tubes n°1 to 3, powder like precipitates were observed after heated for 5 h which means the imine condensation worked fastest in the mixture of o-DCB/ n-BuOH. Tubes n°4 and 5 also showed powder like precipitates but they form more slowly than tubes n°1 to 3. For tubes n°6 and 7, there were no precipitate and this could be due to the use of 1,4-Dioxane. For n°8, a gel like solid was observed. All COFs showed no crystallinity and the highest BET CO of 12.6 cm 3 g -1 and 6.7 cm 3 g -1 , respectively. These data gave further evidence of the high affinity of the materials for CO sorption and selectivity against N2, O2 and CO2. Compared to the reported cobalt complexed POPs, 42 the 2D-COF-CorCo presented a higher ratio of cobalt active site of 56.2 % against 35.2% of 3D-COF-CorCo, which could be assigned to the higher crystallinity and stability of the porous structure, as well as to the regularity and uniformity of the pores distribution. Furthermore, interpenetration of the framework often happens in 3D

COFs 45,46 which should reduce the porosity in the case of 3D-COF-CorCo, and inhibits the accessibility of the cobalt sites and therefore the further binding with CO molecules. The selectivity for CO over O2, N2 and CO2 was determined by IAST calculations according to the fitting parameters deduced from the multisite and single site Langmuir models, considering a gas mixture containing 100 ppm of CO in the other gases (Fig. 21c,d). These conditions were chosen to estimate the suitability of the materials for CO sensing in a real

Synthesis of COFs based on adamantane

Scheme 12. Synthesis of COF-4.

Table 10. Optimization of synthetic conditions for COF-4.

Finally, we prepared the precursor adamantane 43. This compound can be considered as a more rigid analogue of compound 40 (used to prepare 3D COF). Considering the similarity between platforms 40 and 43, we used the same synthetic conditions for optimization (Table 10). However, after verification by PXRD, none of COFs of different tests showed crystallinity.

Furthermore, the porosities are very close to 3D-COF-Cor. This may be a proof that the corrole tends to be a nonlinear linker.

NMR Spectroscopy

NMR solvents were purchased from Eurisotope and were used without further purification. 1 H NMR spectra were recorded on Bruker Avance NEO spectrometers (400 and 500 MHz). All NMR shift values were expressed in ppm. The measurements were made at the PACSMUB-WPCM technological platform, which relies on the "Institut de Chimie Moléculaire de l'Université de Bourgogne" and Welience "TM", a Burgundy University private subsidiary. For free-base corroles, drops of hydrazine were added to remove the presence of any radical corrole and to further enhance the resolution of spectrum. The peak of hydrazine appears at 3.40 ppm in DMSO-d6. For the 1 H NMR of COFs, COFs (10 mg) and DMSO-d6 (500L ) were added in NMR tube. DCl in D2O (7 M, 10 L,  2 eq. of C=N linkages) was added in the tube to decompose COFs. When all solids disappeared, 50 L of hydrazine (64% in H2O, 1.03 g/mL, 15 eq.) was added. The spectra of COFs were carried in 500 MHz spectrometers.

UV-Visible Spectroscopy

All UV-Visible spectra were recorded on a Cary 50 UV-Visible spectrophotometer. All solvents used were of EPR quality. Quartz cells with optical path from 0.1 mm to 10 mm were used.

Standard additions method was used to determine molar attenuation coefficients of new products. The concentrations of all samples were diluted to low level ( 10 -5 mol/L) .

Mass Spectrometry

MALDI-TOF mass spectra were run on a BRUKER Ultraflex II and on a Microflex LRF spectrometers using dithranol as a matrix. High-resolution mass spectra (HRMS) were recorded on a LTQ Orbitrap XL (Thermo) or on an Orbitrap Exploris 240 (Thermo) instruments in the ESI mode.

Infrared Spectroscopy

Infrared spectra were recorded on a IRFT BRUKER Vertex 70v. Sample consisted of pellets ( 3mg of product dispersed in 200 mg of KBr and pressed at 10 tons) which were set up on a P/N 19900 sample holder purchased from Greasby Specac. Baseline were recorded on a pellet of pure KBr (200 mg).

Thermogravimetric analysis

Thermogravimetric (TGA) analyses were recorded using a Netzsch STA 409 PC thermal analyzer. The samples (approximatively 7.0 mg) were heated from 298 to 1273 K with a heating rate of 5 K min -1 under a flow of nitrogen (30 mL min -1 ) and oxygen (10 mL min -1 ).

Adsorption volumetric analysis

Nitrogen adsorption/desorption isotherms were measured at 77 K on a Micromeritics ASAP 2020 instrument. The residual solvent molecules trapped inside the pores of the solids was then removed by degassing the samples (50 -100 mg), transferred in a pre-weighted glass, in a dynamic vacuum at 298 K for at least 5 h before measurements. The specific surface area was determined using the Langmuir and the Brunauer-Emmett-Teller (BET) calculations, and the pore volumes were obtained directly from the N2 adsorption/desorption isotherms at P/P0 = 0.99.

To avoid large discrepancies between the two values of the surface area due to the invalid BET assumption for microporous solids over the usual range 0.05 < P/P0 < 0.25, a suitable pressure range was applied using a range that gives increasing values of VN2(P0-P) with P/P0 as required by the groups of Snurr 1 and Rouquerol. 2 Based on the consistency of this criteria, the pressure range used for the BET surface area calculations was then 1.5  10 -3 < P/P0 < 0.05. The pore size was determined using the Horvath-Kawazoe (HK) equation with the Saito-Foley model.

Low-pressure gas adsorption measurements for CO2, N2, and CO at 298 K were run on the same apparatus. The sample temperature was maintained using a Lauda cooler circulator and a double circulating jacket connected to a thermostatic bath in which the sample tube was dipped.

Scanning electron microscopy

The

Energy dispersive X-ray spectroscopy (EDS)

EDS measurements were performed on a Hitachi SU8230 Field Emission Scanning Electron Microscopy apparatus equipped with an Oxford EDS detector and having resolution of 0.8 nm @ 15KV / 1.1 nm @ 1KV. Measurements were conducted at DimaCell Imaging Center facilities (INRAE, University of Burgundy Franche-Comté).

Inductively coupled plasma atomic emission spectroscopy (ICP-AES)

All Metal quantifications (Co, Zn, etc…) were carried out with an ICP-AES iCAP 7400, samples were prepared by microwaving up to 10 mg of POPs into a solution of pure nitric acid.

Elementary analysis

The organic content of all samples was determined from CHNS elemental analysis performed on a FTA/Thermofinningan Flash 1112 analyser.

Material Studio

The geometry optimization of lattice structure and refinement of PXRD pattern were performed at forcite module and reflex module in Material Studio, respectively. Thanks for the help from Prof. Bao Zhang from -School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China.

Powder X-ray diffraction

Powder X-ray diffraction (PXRD) experiments were performed on an Empyrean diffractometer from the PANalytical company in the range 2° < 2θ < 50°. The uncrushed samples were placed between two Mylar sheets and the analyses were performed in transmission mode using a focusing X-ray mirror equipped with fixed divergent and anti-scattering slits (aperture 0.5°) and 0.02 rad Soller slits. The data collection was run with a copper anticathode X-ray tube (CuKα1 = 1.54060 Å / CuKα2 = 1.54443 Å) and with a PIXcel 3D detector equipped with an antiscattering slit of 5 mm.

B. Synthetic procedures

The synthesis protocols of all compounds including dipyrromethanes, corroles, platforms and porous materials are presented in detail in this part.

4-(Benzyloxycarbonyl)benzaldehyde (3) 4

The procedure from literature was slightly modified. A solution of 4-formylbenzoic acid (9.00 g, 60.0 mmol, 1 eq) and K2CO3 (16.6 g, 120.0 mmol, 2 eq) in DMF (120 mL) was added benzyl bromide (12.3 g, 72 mmol, 1.2 eq) slowly. After completion of addition, the reaction was stirred at RT for 12 h. Water was added and extracted with EtOAc for 3 times. The combined organic layers were washed with brine and dried over magnesium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography (Silica, CHCl3/heptane = 3:7), giving compound as colorless oil. To keep it stable, the compound was stored under argon atmosphere.

Yield: 12.3 g (85%)

5-[4-(5,5-Dimethyl-1,3-dioxan-2-yl)phenyl]dipyrromethane (5)

The synthesis of compound 5 was already reported in the literature. 7 However, the procedure used to synthesize compound 5 is based on general procedure for the synthesis of dipyrromethanes (Method A). Compound 5 was obtained by using compound 2 (22.0 g, 0.10 mol, 1 eq) and freshly distillated pyrrole (545 mL, 7.86 mol, 78.6 eq). The TFA (985 L, 11.5 mmol, 0.12 eq) was added slowly. After 1 h, powder NaOH (13.0 g, 3.25 mol, 32.5 eq) was added to quench the reaction. The mixture was filtered on celite and the pyrrole was recovered.

The crude compound was purified on a silica gel plug with DCM as eluent and further recrystallization from mixture of THF and heptane, giving colorless solid.

Yield: 24.0 g (71%)

5-(Pentafluorophenyl)dipyrromethane (9) 6

The synthesis of dipyrromethane 9 was carried out by a modification of the procedure reported by Laha et al. 6 , using general procedure for the synthesis of dipyrromethanes (Method B). For the reaction, pentafluorobenzaldehyde (9.80 g, 50 mmol, 1 eq) and freshly distillated pyrrole (347 mL, 5.00 mol, 100 eq) were used. Further recrystallization gives colorless powder.

Yield: 15.0 g (96%) The corrole 20 is not described. In a round bottom flask, a solution of corrole 19 (105 mg, 0.16 mmol, 1 eq) and cobalt acetylacetonate (43.7 mg, 0.17 mmol, 1.05 eq) in dimethylsulfoxide

was degassed with argon. The mixture was heated at 80°C for 40 min under argon and the reaction was monitored by mass spectrometry. After cooling, the mixture was poured into degassed water and diluted HCl solution (0.1M) was added to precipitate the cobalt complex.

The corrole complex was collected by centrifugation and washed with water 2 times, dried under vacuum, giving pure compound.

Yield: 99 mg (78%) 8.39-8.33 (m, 10H), 8.29-8.27 (m, 2H), 2.68 (s, 6H).

13 C NMR (125 MHz, MeOD-d4, 10 L Hydrazine) δ 175. 7, 146.9, 145.5, 142.9, 141.5, 140.0, 137.2, 135.3, 135.2, 132.8, 131.0, 129.1, 128.8, 128.1, 124.9, 117.4, 115.7, 108.8, 40.4.

FTIR (KBr, cm -1 ): 3068 (broad peak, OH carboxyl), 1699 (C=O carboxyl), 1014 (S=O DMSO).

1,3,5,7-Tetrakis-4-formylphenyladamantane (43)

The compound was synthesized according to the literature. 26 To a 250 mL round bottom flask, adamantane 41 (1.20 g, 2.72 mmol, 1 eq) and 150 mL dry dichloromethane was added under argon. The mixture was stirred and cooled to -10°C. TiCl4 (6.00 mL, 54.4 mmol, 20 eq) was slowly added to the mixture and stirred at -10°C for 30 min.

Then, dichloromethyl methylether (3.90 mL, 43.5 mmol, 16 eq) was subsequently added dropwise to the mixture. The reaction was kept at -10°C for 3 h and then allowed to warm to room temperature and stirred overnight. The mixture was poured into 100 mL ice-water, and 33 mL of 1 M HCl was added and allowed to stir for 30 minutes. The two-phase mixture was separated, and the aqueous phase was washed twice with DCM. The combined organic phases were successively washed with saturated aqueous NaHCO3 and saturated NaCl and then dried with Na2SO4. Solvents were removed and the resultant was purified by column chromatography (Silica, DCM:MeOH = 98:2), giving pure compound.

Yield: 1.0 g (67%)

Truxene (45)

Compound 45 was synthesized according to the literature with a slight modification. 28 1-Indanone (8.90 g, 67.3 mmol, 1 eq) was dissolved in 40 mL of acetic acid, and then 20 mL of concentrated hydrochloric acid was added. The solution was heated to 100 °C and stirred for 16 h, until it turned into yellow colored suspension. The hot mixture was poured into 500 ml of saturated sodium carbonate aqueous solution with ice, and stirred for 1 h. The yellow precipitate was filtered, and washed with water, acetone and dichloromethane to give a white powder.

Yield: 6.00 g (80%). The compound was synthesized according to the literature with a slight modification. 29 To a solution of 46 (3.40 g, 5.00 mmol, 1 eq) in DCM (50 mL), bromine (1.8 mL, 35.1 mmol, 7 eq) was added slowly at 0°C, covered from light. After 12 h, the reaction was quenched with saturated sodium thiosulfate solution and brine to remove excess bromine. The mixture was extracted with DCM, and organic layer was washed with Na2CO3 solution and dried with MgSO4. After removal of the solvent, a solid residue was afforded. The crude product was purified by flash column chromatography (Silica, heptane), giving a yellow solid.

Yield: 4.38 g (93%)

1 H NMR (300 MHz, CDCl3) δ 8.19 (d, J = 8.5 Hz, 3H), 7.57 (d, J = 2.0 Hz, 3H), 7.52 (dd, J = 8.5 Hz, J = 2.0 Hz, 3H), 2.91-2.81 (m, 6H), 2.09-1.99 (m, 6H), 1.0-0.80 (m, 12H), 0.59-0.34 (m, 30H).

Synthesis of COFS based on cobalt corroles COF-1

A Schlenk tube was charged with aldehyde corrole 14 (72.8 mg, 0.11 mmol, 2 eq) and platform 38 (21.3 mg, 0.055 mmol, 1 eq) in a mixed solution of 1,4-Dixane (5.6 mL) and 6 M aqueous acetic acid (0.56 mL). The mixture was sonicated for 10 min to completely solubilize the starting materials. Then the Schlenk tube was sealed and the mixture was flash frozen at 77 K (liquid N2 bath), followed by three freeze-pump-thaw cycles and sealed under vacuum. The reaction mixture was heated at 120 °C for 3 days to afford a dark precipitate which was isolated by centrifugation and washed by THF several times. The product was dried under vacuum for 24 hours to afford dark powder.

Yield: 20 mg (21%). FTIR (KBr, cm -1 ): 1616 (C=N imine bond).

2D-COF-Cor

A Schlenk tube was charged with amino corrole 16 (462 mg, 0.74 mmol, 1.5 equiv.) and 1,3,5triformylbenzene (80.0 mg, 0.49 mmol, 1 equiv.) in a mixed solution of n-butanol (32.0 mL), mesitylene (16.0 mL) and 6 M aqueous acetic acid (3.2 mL). The mixture was sonicated for 10 min to completely solubilize the starting materials. Then the Schlenk tube was sealed and the mixture was flash frozen at 77 K (liquid N2 bath), followed by three freeze-pump-thaw cycles and sealed under vacuum. The reaction mixture was heated at 120 °C for 3 days to afford a dark precipitate which was isolated by centrifugation and washed by THF several times. The product was dried under vacuum for 24 hours to afford dark powder.

Yield: 420 mg (81%). Elementary analysis (%): calculated for C47H29F3N6 : C 76.83, H 3.98, N 11.44; found: C 73.67, H 3.78, N 11.32.

FTIR (KBr, cm -1 ): 3368 (NH2, corrole), 1699 (C=O, platform), 1614 (C=N imine bond).

COF-2

A Schlenk tube was charged with aldehyde corrole 16 (22.3 mg, 0.036 mmol, 1.5 eq) and platform (5 mg, 0.024 mmol, 1 eq) in a mixed solution of n-BuOH (2 mL), mesitylene (1 mL) and 6 M aqueous acetic acid (0.2 mL). The mixture was sonicated for 10 min to completely solubilize the starting materials. Then the Schlenk tube was sealed and the mixture was flash frozen at 77 K (liquid N2 bath), followed by three freeze-pump-thaw cycles and sealed under vacuum. The reaction mixture was heated at 120 °C for 24 h to afford a dark precipitate which was isolated by centrifugation and washed by THF several times. The product was dried under vacuum for 24 hours to afford dark powder.

Yield: 24.6 mg (90%).

FTIR (KBr, cm -1 ): 1631 (C=O keto stretch), 1600 (C=C keto stretch), 1278 (C-N keto form).

COF-3

A Schlenk tube was charged with aldehyde corrole 16 (16.6 mg, 0.027 mmol, 1.5 eq) and platform (13.7 mg, 0.018 mmol, 1 eq) in a mixed solution of n-BuOH (1.5 mL), mesitylene (1.5 mL) and 6 M aqueous acetic acid (0.2 mL). The mixture was sonicated for 10 min to completely solubilize the starting materials. Then the Schlenk tube was sealed and the mixture was flash frozen at 77 K (liquid N2 bath), followed by three freeze-pump-thaw cycles and sealed under vacuum. The reaction mixture was heated at 120 °C for 24 h to afford a dark precipitate which was isolated by centrifugation and washed by THF several times. The product was dried under vacuum for 24 hours to afford dark powder.

FTIR (KBr, cm -1 ): 1618 (C=N imine bond). 2D-COF and 3D-COF based on corroles were obtained and characterized We found that 3D COF showed no crystallinity while 2D COF is highly crystalline. For CO sorption, 2D COF showed higher affinity and selectivity for CO than 3D COF. What's more, 2D COF showed higher selectivity for CO vs CO2, O2, N2 which are interference gas for sensors.

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