Bipyridines functionalised with acrylic functions, methods for preparing same and uses thereof

Abstract

The invention relates to hybrid polymer / filler materials prepared from bipyridine derivatives functionalised with acrylate groups of formula (I) and / or metal complexes comprising said functionalised bipyridine derivatives, wherein the polymer comprising the functionalised bipyridines can form a shell around the filler, as well as to the method for preparing same and the uses thereof.

Description

[0001] BIPYRIDINES FUNCTIONALIZED BY ACRYLIC FUNCTIONS, THEIR PREPARATION PROCESSES AND THEIR USES

[0002] TECHNICAL FIELD OF THE INVENTION

[0003] The invention relates to polymer / filler hybrid materials prepared from bipyridine derivatives functionalized with acrylate groups, wherein the polymer of the hybrid material comprises the functionalized bipyridines and can form a shell around said filler, as well as hybrid materials comprising at least one transition metal, their preparation process and their uses.

[0004] STATE OF THE ART

[0005] 2,2'-Bipyridine ligands consist of two pyridines whose nitrogen atoms have a strong bonding affinity for metals, particularly transition metals. Consequently, they have been extensively studied for the complexation of metal ions. 2,2'-Bipyridine is a neutral ligand that can form a charged complex with cationic metals. Therefore, 2,2'-Bipyridine ligands are sought after in numerous fields, including coordination chemistry, supramolecular chemistry, photochemistry, and materials chemistry. 2,2'-Bipyridine ligands may also find promising applications in the development of metal-based drugs, for example, as therapeutic agents, diagnostic agents, medical imaging agents, or drug delivery systems.

[0006] Another potential use of 2,2'-bipyridine ligands is in catalysis, where bipyridine complexes can be used as catalysts and photocatalysts for various chemical reactions, such as oxidation, reduction, and cross-coupling reactions, with potential applications in photocatalytic water separation, carbon dioxide reduction, organic synthesis, and pollutant degradation. However, conventional 2,2'-bipyridine ligands, when used in catalysis, are difficult to recover and recycle.

[0007] These varied applications imply that the properties of bipyridine can be fine-tuned according to the intended use. For example, its polymerization capacity is generally adjusted, notably by introducing functional groups onto the pyridine rings.

[0008] The article by A.S. Maier et al., Macromolecules, 55 (2022) 7039–7048, describes the preparation of a 2,2'-bipyridine-based ligand functionalized with a vinyl group, as well as the Lewis-pair-catalyzed polymerization of the ligand and the complexation of the resulting polymer with rhenium and ruthenium. The article by M. Antonietti et al., Macromol. Rapid Commun. 16 (1995) 283–289, describes a microemulsion process for preparing a linear copolymer using 6'-methyl-2,2'-bipyridin-6-ylmethyl methacrylate and a crosslinking agent.

[0009] WO2019 / 097021 describes bifunctional silane-based photoinitiators that can be used for the preparation of polymers by photopolymerization.

[0010] However, existing bipyridine derivatives are synthesized using costly, complex methods that are difficult to implement on an industrial scale. Indeed, the introduction of functional groups onto pyridines can affect the complexation rate and / or the polymerization efficiency of these ligands, depending on their nature and position.

[0011] Existing polymerization processes are therefore poorly suited to certain applications.

[0012] There is therefore a need for a synthesis process for functionalized bipyridines that allows obtaining bipyridine derivatives functionalized with desired acrylate groups and a polymerization process that can be generalized to the various uses of bipyridine-based materials.

[0013] In particular, there is a need for bipyridine-based materials that exhibit good catalytic activity, good stability and / or are easily recoverable, or even recyclable, from a reaction medium.

[0014] DESCRIPTION OF THE INVENTION

[0015] The present invention aims to remedy all or part of the drawbacks of the prior art mentioned above.

[0016] To this end, the inventors have developed a new process using a bipyridine derivative functionalized with acrylate groups whose complexation and / or polymerization properties are improved, while exhibiting good stability properties.

[0017] An object of the present invention consists of a process for preparing a hybrid material comprising a photopolymerization step in which a filler, a photoinitiator and at least one compound of formula (I) as described below are reacted.

[0018] in which,

[0019] - Ri, R2, R4 and R5, whether identical or different, independently represent a hydrogen or an alkyl group,

[0020] - R3 and Re, whether identical or different, independently represent a hydrogen or an alkyl group, or R3 and Re are linked by a single bond and jointly represent a -(CH2) group P - (CH2)q- in which p+q = 1 or 2, p being an integer varying from 0 to 2, q being an integer varying from 0 to 2, and p and q not being simultaneously nus, or R3 and Re are linked by a double bond and jointly represent a group -CH2-CH=CH-CH2-;

[0021] - R? and Rs, whether identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, a halogen, or a group of formula C m X 2m+i , where X is a halogen and m is an integer ranging from 1 to 6;

[0022] - R9 and R10, whether identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, a halogen, or a group of formula C m X 2m+i in which X is a halogen and m is an integer ranging from 1 to 6;

[0023] - R11 and RI2, whether identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, a halogen, or a group of formula C m X 2m+ i, where X is a halogen and m is an integer ranging from 1 to 6;

[0024] - R13 and R14, which are identical, represent an alkyl group or an alkoxy group;

[0025] - n is an integer ranging from 0 to 1, it being understood that when n = 0 the acrylate group is directly bonded to the pyridine ring, and that when n = 1 the acrylate group is bonded to R13 or R14; as well as their preparation methods. In a preferred embodiment of the present invention, the photoinitiator is of the silane type and the filler is, prior to the photopolymerization step, bonded to the silane-type photoinitiator.

[0026] In a preferred embodiment of the present invention, the process for preparing a hybrid material includes, prior to the photopolymerization step, a complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal.

[0027] In a preferred embodiment of the present invention, the process for preparing a hybrid material comprises, subsequent to the photopolymerization step, a complexation step in which the hybrid material obtained in the photopolymerization step is reacted with at least one transition metal.

[0028] In a preferred embodiment of the present invention, the process for preparing a hybrid material comprises:

[0029] - prior to the photopolymerization step, a complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal;

[0030] - the photopolymerization step in which the compound obtained in the complexation step is reacted with a compound of formula (I) in the presence of the filler and the photoinitiator; and

[0031] - subsequent to the photopolymerization step, another complexation step in which the hybrid material obtained in the photopolymerization step is reacted with at least one transition metal.

[0032] The invention also relates to a hybrid material that can be obtained by the process which is the subject of the present invention.

[0033] In a preferred embodiment of the present invention, the hybrid material comprises at least one transition metal, preferably two transition metals.

[0034] The invention also relates to the use of hybrid materials, particularly as catalysts.

[0035] The invention aims in particular to provide a catalyst that can be easily recovered, or even recycled, from a reaction medium and / or that has good catalytic activities, good stability properties and / or good properties for converting light energy.

[0036] BRIEF DESCRIPTION OF THE FIGURES

[0037] Figure 1 shows the kinetics of photopolymerization during the synthesis of the hybrid materials in Examples 5 and 6. Figure 2 shows the powder X-ray diffraction (PXRD) spectra of pure zeolite, zeolite grafted with (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-1-one and the hybrid materials prepared in Examples 5 and 6.

[0038] Figure 3 shows the Fourier transform infrared (FTIR) spectroscopy spectra of pure zeolite, zeolite grafted with (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-l-one and hybrid materials prepared in Examples 5 and 6.

[0039] Figure 4 represents the N2 adsorption / desorption isotherm on the pure zeolite and on the hybrid material prepared in Example 9.

[0040] Figure 5 represents the CO2 absorption isotherm on pure zeolite and on the hybrid material prepared in Example 9.

[0041] Figure 6 represents the evolution of the amount of CO produced during the photocatalytic reduction of CO2 under visible light (LED 405 nm) on the hybrid materials prepared in examples 9 and 10.

[0042] Figure 7 represents the evolution of the amount of CO produced during the photocatalytic reduction of CO2 catalyzed by the hybrid material prepared in example 9.

[0043] Figure 8 represents the powder X-ray diffraction (PXRD) spectra of pure MOF, MOF grafted to (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-1-one, MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) and MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl) hybrid materials obtained in Example 15.

[0044] Figure 9 represents the Fourier transform infrared (FTIR) spectra of pure MOF, MOF grafted to (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-1-one, MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material and MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl) hybrid material obtained in Example 15.

[0045] Figure 10 represents the CO2 absorption isotherm on pure MOF and on the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl hybrid material prepared in Example 15.

[0046] Figure 11 represents the absorption isotherm of N2 on pure MOF and on the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl hybrid material prepared in Example 15.

[0047] Figure 12 represents the evolution of the amount of CO produced over time during the reduction of CO2 photocatalyzed by the hybrid material MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-dacrylate]Re(CO)3Cl) prepared in example 15.

[0048] Figure 13 shows the rotation frequency and number of rotations of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl hybrid material prepared in Example 15 during the photocatalyzed reduction of CO2. Figure 14 shows the cyclic voltammograms recorded under an argon atmosphere of the reference catalyst (curve (a)) and of the rhenium-containing hybrid material obtained in Example 15 (curve (b)).

[0049] Figure 15 shows the cyclic voltammograms of the reference catalyst recorded under an argon atmosphere (curve (a)) or under a CO2 atmosphere (curve (b)).

[0050] Figure 16 shows the cyclic voltammograms of the rhenium-containing hybrid material obtained in Example 15, MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl), recorded under an argon atmosphere (curve (a)) or under a CO2 atmosphere (curve (b)).

[0051] DETAILED DESCRIPTION OF THE INVENTION

[0052] It has been found that the functionalization of a 2,2'-bipyridine compound with acrylate groups in the 4,4' position makes it possible to obtain a functionalized compound which, due to its structure, is able to be polymerized, in particular photopolymerized, with a high yield, and to be immobilized on an inorganic or organometallic filler, for example by using a bifunctional coupling agent as a photoinitiator.

[0053] It was also found that the 2,2'-bipyridine compound functionalized with acrylic groups according to the invention can complex with transition metals in high yield, and that it retains this ability even when immobilized on a charge. Indeed, the 2,2'-bipyridine compound functionalized with acrylic groups is capable of complexing with a transition metal, despite the steric hindrance induced by the presence of two acrylic groups at positions 4 and 4' of the bipyridine ring.

[0054] It was also found that the hybrid materials obtained from said compound 2,2'- bipyridine functionalized with acrylic functions according to the invention advantageously exhibit catalytic activity.

[0055] In particular, these hybrid materials were found to be catalysts capable of functioning in heterogeneous phases and to be more easily prepared and recovered from the reaction medium, thus facilitating their recycling. These hybrid materials were also found to exhibit high selectivity, good adaptability, and stability in the presence of moisture and / or irradiation.

[0056] These hybrid materials are an object of the present invention. These hybrid materials, also referred to herein as the hybrid materials according to the invention, advantageously stabilize, or at best preserve, the structure of the load. The hybrid materials according to the invention advantageously preserve the accessibility of the load, in particular the accessibility of the pores of a porous load. In other words, the hybrid materials according to the invention can advantageously capture molecules such as oxidants or reducers, in particular CO2, and concentrate said molecules at the active sites of the hybrid materials according to the invention.

[0057] Another object of the present invention relates to a process for synthesizing the hybrid material which is simple to implement, non-toxic and suitable for implementation on an industrial scale.

[0058] In the rest of the description, the terms "acrylic function", "acrylate function", "acrylic group" or "acrylate group" will be used interchangeably.

[0059] The term "comprising" is understood, for the purposes of this description, as encompassing the terms "containing", "made up of" or "consisting of".

[0060] The terms "made of" or "consisting of", as used in this description, exclude the presence of any characteristics other than those that follow this formulation.

[0061] Unless otherwise stated, the value ranges indicated include the limits.

[0062] The term "polymer" refers, unless otherwise stated, to the polymer of the hybrid material.

[0063] < Compound of fprmule.fj). or.derived from functional bipyridine

[0064] The functionalized bipyridine derivative of formula (I) useful to the present invention is a compound of formula (I) in which,

[0065] - Ri, R2, R4 and R5, identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms;

[0066] - R3 and Re, identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, or Rs and Re are linked by a single bond and together represent a -(CH2) group P - (CH2) q -in which p+q = 1 or 2, p being an integer varying from 0 to 2, q being an integer varying from 0 to 2, and p and q not being simultaneously nus, or R3 and Re are linked by a double bond and jointly represent a group -CH2-CH=CH-CH2-;

[0067] - R? and Rs, whether identical or different, independently represent a hydrogen atom, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula C m X 2m+i , where X is a halogen and m is an integer ranging from 1 to 6;

[0068] - R9 and R10, whether identical or different, independently represent a hydrogen, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula C m X 2m+i , where X is a halogen and m is an integer ranging from 1 to 6;

[0069] - R11 and RI2, whether identical or different, independently represent a hydrogen, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula C m X 2m+i in which X is a halogen and m is an integer ranging from 1 to 6;

[0070] - R13 and R14, identical, represent a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms or an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms;

[0071] - n represents an integer varying from 0 to 1, the acrylate function being directly linked to the pyridine ring when n is 0 and the acrylate function being linked to R13 or R14 when n is 1.

[0072] By "linear or branched alkyl, saturated or unsaturated, comprising 1 to 6 carbon atoms", we mean, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, neo-pentyl, hexyl, isohexyl, sec-hexyl or tert-hexyl group, or an alkenyl group such as an ethenyl or vinyl, propenyl or allyl, 1-propenyl, n-butenyl, iso-butenyl, 3-methylbut-2-enyl, n-pentenyl, hexenyl, etc.

[0073] By "halogen" we mean an atom of fluorine, chlorine, bromine or iodine.

[0074] Preferably, in formula (I) above, n is equal to 0 and Ri, R2, R3, R4, R5, Re, R7, Rs, R9, R10, R11 and RI2 are as defined above. The compounds of formula (I) then correspond to formula (IA) below:

[0075] (lA) According to another preferred aspect, in formula (I) above, n is equal to 1, Ri, R2, R3, R4, R5, R6, R7, Rs, R9, R10, R11 and R12 are as defined above and R13 and R14 represent a linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, preferably CH2.

[0076] Advantageous compounds of formula (I) are those in which n equals 1, Ri, R2, R3, R4, Rs, Re, R7, Rs, R9, R10, R11 and R12 are as defined above and R13 and R14 represent

[0077] CH2. These compounds correspond to the formula (1B) below:

[0078] (lB) Advantageously, functionalized 2,2'-bipyridine derivatives of formula (I) may contain two identical or different acrylic functions.

[0079] Compounds of formula (I) in which Ri, R2, R3, R4, R5 and Re and / or R7, Rs, R9, R10, Ru and RI2 represent hydrogen are advantageous compounds of the invention.

[0080] Other compounds of formula (I) in which

[0081] - Ri, R2, R3, R4, Rs, Re, R7, Rs, R9, R10, R11, R12 are identical, represent a hydrogen and n = 0, or

[0082] - Ri, R2, R3, R4, Rs, Re, R7, Rs, R9, R10, R11 and RI2 identical, represent a hydrogen, n = 1 and R13 and R14 represent CH2, are also advantageous compounds according to the invention.

[0083] .<Preparation processes, of the compound of formula _(l ) . > The compound of formula (I) as defined above in which

[0084] - Ri, R2, R3, R4, Rs, Re, R13, R14 and n, are as defined above;

[0085] - R? and Rs are as defined above and are identical.

[0086] - R9 and R10 are as defined above and are identical, and

[0087] - R11 and R12 are as defined above and are identical, can be obtained by a process comprising: the reaction of a compound of formula (II) with an acrylic acid derivative of formula (III)

[0088] (III) in which

[0089] - Ri, R2, R3, R4, Rs, Re, R7, R9, R11, R13, R14 and n, are as defined above;

[0090] - X is a halogen, in the presence of a base and an organic solvent, the acrylic acid derivative and the base being in excess relative to the compound of formula (II).

[0091] According to one aspect of the process, R7, Rs, R9, R10, R11 and R12 are identical, and represent, in particular, hydrogen.

[0092] For example, a base such as diisopropylethylamine (DIPEA) or triethylamine (TEA) will be used.

[0093] The organic solvent can be chosen, for example, from dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), chloroform, dicholoromethane or tetrachloromethane.

[0094] The excess of acrylic acid derivative relative to compound of formula (II) may, for example, be between 5 and 8 equivalents of acrylic acid derivative per 1 equivalent of compound of formula (II), in particular 5 to 7 equivalents of acrylic acid derivative per 1 equivalent of compound of formula (II), in particular 7 equivalents of acrylic acid derivative per 1 equivalent of compound of formula (II). The excess of base relative to compound of formula (II) may, for example, be between 5 and 8 equivalents of base per 1 equivalent of compound of formula (II), in particular 5 to 7 equivalents of base per 1 equivalent of compound of formula (II).

[0095] The compound of formula (I) as described above

[0096] (I) in which Ri, F, R3, R4, Rs, Re, R7, Rs, R9, R10, Ru, R12, R13, R14 and n are such as defined above, and at least one of the substituents R7, R9 and Ru is different from at least one of the substituents Rs, R10 and R12, can be obtained by a process comprising a step of preparation of the compound of formula (VI)

[0097] in which

[0098] - Ri, R2, R3, R4, Rs, Re, R7, R9, Ru, R13, R14 and n are as defined above; - R15 represents a protecting group, in particular a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, unsubstituted or substituted by a halogen; an alkoxy group in which the alkyl group is linear or branched, saturated or unsaturated, comprising 1 to 6 carbon atoms, unsubstituted or substituted by a halogen; an aryl group whose ring comprises 3 to 10 carbon atoms, unsubstituted or substituted by at least one linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms; or an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms;or a silyl group, unsubstituted or substituted by at least one linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms or by an aryl group whose ring comprises 3 to 10 carbon atoms, unsubstituted or substituted by at least one linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms; by the reaction of a compound of formula (V);

[0099]

[0100] (V) in which Ri, R2, R3, R4, Rs, Re, R13, R14, R15 and n are such as defined above for formula (I); with an acrylic acid derivative of formula (III) in which

[0101] - R7, R9, and R11 are as defined above for formula (I); - X is a halogen, in the presence of a base and an organic solvent, the acrylic acid derivative and the base being in excess relative to the compound of formula (V); a step of preparing the compound of formula (VII) from the compound of formula

[0102] (VI) by eliminating the protective group R15

[0103] in which Ri, R2, R3, R4, Rs, Re, R7, R9, Ru, R13, R14 and n are such as defined above; and

[0104] - the reaction of the compound of formula (VII) with an acrylic acid derivative of formula (IV)

[0105] (IV) in which

[0106] - Rs, R10 and R12, are as defined above;

[0107] - X is a halogen; in the presence of a base and an organic solvent, the acrylic acid derivative and the base are in excess relative to the compound of formula (VII).

[0108] In particular, by "aryl group" we mean for example a benzyl, a phenyl, a tolyl, a xylyl or a naphthyl.

[0109] In particular, the compound of formula (V) may correspond to the compound of formula (II) in which one of the two alcohol functions is protected by a protecting group R15.

[0110] In particular, the protecting group R15 is chosen such that O-R15 forms an acetal, an aryl ether, or a silyl ether.

[0111] In particular, when O-R15 forms a silyl ether, R15 can be selected from trimethylsilyl (TMS), triethylsilyl (TES), tert-butyldimethylsilyl (TBS or TBDMS), tert-butyldiphenylsilyl (TBDPS), or triisopropylsilyl (TIPS), preferably trimethylsilyl (TMS). In this case, the compound of formula (VII) can, for example, be prepared from a reaction between the compound of formula (VI) in the presence of an F- anion followed by an acidification reaction.

[0112] In particular, when O-R15 forms an aryl ether, preferably a benzyl ether, R15 may be an aryl group whose aromatic ring comprises 3 to 10 carbon atoms, unsubstituted or substituted by at least one linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, or an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms. Preferably, R15 is a benzyl group. In this case, the compound of formula (VII) may, for example, be prepared by palladium-catalyzed hydrogenation deprotection of the compound of formula (VI).

[0113] In particular, when O-R15 forms an acetal, R15 can be a halogen-substituted methyl group or an optionally cyclic alkoxy group whose alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms. For example, R15 can be a methyl chloromethyl ether (MOM-Cl) group or an oxane such as tetrahydropyran (THP).

[0114] In particular, when R15 is tetrahydropyran (THP), compound (V) can be prepared by reacting dihydropyran with compound (II) in the presence of an acid, such as para-toluenesulfonic acid, in an organic solvent, such as chloroform. Compound (VII) can be prepared by deprotection from compound (VI) in the presence of an acid, such as para-toluenesulfonic acid, in an organic solvent, such as methanol.

[0115] The conditions for deprotection (removal of the R15 protective group) mentioned above are usual in the field.

[0116] The general and particular aspects relating to the base, solvent and acrylic derivative, as defined above for the process of preparing a compound of formula (I) as described above, in which R7 and Rs are identical, Rg and R are identical and Ru and R12 are identical, also apply to the process of preparing a compound of formula (I) in which R7, Rs, R9, R10, Ru and R12 are not all identical.

[0117] Preferably, in the process for preparing the compound of formula (I), at least one of the following conditions is met:

[0118] - the base is triethylamine (TEA);

[0119] - the reaction of the acrylic acid derivative of formula (III) or (IV) with the compound of formula (II), (V) or (VII) is carried out at a temperature greater than or equal to 20°C and less than or equal to 60°C;

[0120] - the reaction of the acrylic acid derivative of formula (III) or (IV) with the compound of formula (II), (V) or (VII) is carried out at a pH between 8 and 14, preferably between 9 and 14, in particular between 10 and 14, more particularly between 9 and 12; - the organic solvent is chloroform;

[0121] - the derivative of acrylic acid is acryloyl chloride.

[0122] In particular, the compound of formula (I) as defined above can be obtained by a process which is simple, non-toxic, suitable for industrial implementation, and which yields a product of high purity.

[0123] <Charge>

[0124] The payload for the present invention may be porous or non-porous. In particular, the payload is an inorganic particle, for example a metal-organic structure, a silicate, a silica or a metal oxide, preferably a zeolite.

[0125] In particular, the metal-organic structure, also called a metal-organic framework (MOF), is preferably titanium- or zirconium-based. When the filler is a metal-organic structure, it is, for example, of the Universitetet i Oslo (UiO-66), MIL-125, MIL-100, MIL-101, MIL-177 type and their derivatives. Advantageously, this filler is a porous filler whose pores may contain an organic molecule, in particular a metal ion or a fluorescent molecule.

[0126] .< .Ph.Qt am o rçeu r or . ag en. t de cou u .lag e>

[0127] The photoinitiator useful for the present invention, in addition to its role of initiating or enabling the photopolymerization of at least the compound of formula (I), also acts as a coupling agent between the polymer formed, in particular from the functionalized bipyridine derivative of formula (I), and the filler. The photoinitiator is preferably of the silane type, and more particularly a bifunctional silane.

[0128] In particular, the photoinitiator can be any photoinitiator as described in WO2019 / 097021.

[0129] In particular, the photoinitiator can be a compound with the following formula (A): in which:

[0130] - Ri represents an alkylene group comprising 1 to 6 carbon atoms or an - O-alkylene group comprising 1 to 6 carbon atoms;

[0131] - R2 and R3, identical or different, are chosen from the group consisting of: H, NO2, OR a SR a and NR aRb, Ra and Rb, identical or different, representing H or an alkyl group comprising 1 to 6 carbon atoms, or R2 and R3 can together form, with the carbon atoms that bear them, a phenyl group;

[0132] - n is 0, 1, 2 or 3;

[0133] - R4 is chosen from the group consisting of: NO2, OR a SR a and NR a Rb, Ra and Rb being as defined above;

[0134] - R5 and Re, whether identical or different, represent an alkyl group comprising 1 to 6 carbon atoms or an alkoxy group comprising 1 to 6 carbon atoms; and

[0135] - R7, Rs and R9, identical or different, represent an alkyl or alkoxy group comprising 2 to 6 carbon atoms.

[0136] In particular, the photoinitiator has formula (A) with n=0.

[0137] In particular, the photoinitiator has the formula (A) with R5 and Re representing a methyl group.

[0138] In particular, the photoinitiator has the formula (A) with R7, Rs and R9 representing an ethyl group.

[0139] In particular, the photoinitiator has the following formula (A-1):

[0140] (A-1 ) in which Ri; R2 and R3 are such as defined in formula (A).

[0141] The photoinitiator is preferably SPI-1, namely 2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-l one, described in application WO2019 / 097021.

[0142] <Métal de Transition> The transition metal useful to the present invention is, in particular, chosen from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium, rhenium or iridium, more preferably ruthenium or rhenium.

[0143] < Hybrid material preparation process >

[0144] The process for preparing the hybrid material includes a photopolymerization step in which the filler, the photoinitiator and at least one compound of formula (I) as defined above are reacted.

[0145] <greffage>

[0146] In a preferred embodiment of the invention, the process includes, prior to the photopolymerization step, a loading grafting step in which the photoinitiator is immobilized on the loading, or in other words, in which the loading is bonded to the photoinitiator. This grafting step can be carried out in the presence of a solvent, such as ethanol, and under stirring at a temperature above ambient temperature, in particular at 120°C.

[0147] Preferably, the charge is, prior to the photopolymerization step, bound to the silane-type photoinitiator.

[0148] < Complexation of the compound of formula (I) prior to photopolymerization >

[0149] The process for preparing a hybrid material may include a complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal to obtain a metal complex of the compound of formula (I). The complexation step of the compound of formula (I) is carried out prior to the photopolymerization step.

[0150] The metal complex, also called the metal complex of the compound of formula (I) therefore includes a compound of formula (I) as described above and at least one transition metal.

[0151] The metal complex can be prepared by a conventional method, by reacting the compound of formula (I) with the transition metal in an organic solvent at reflux temperature. Reference may be made, for example, to the preparation of metal complexes of unfunctionalized 2,2'-bipyridine compounds described in H. Nasrallah, et al., Journal of Catalysis, 404 (2021), 46-55.

[0152] In a preferred embodiment of the present invention, during the complexation step of the compound of formula (I), a compound of formula (I) is reacted with ruthenium, in particular cis-Dichlorobis(bipyridine)ruthenium(I) of formula Ru(bpy)2Cl2. < Photopolymerization >

[0153] Preferably, the photopolymerization step is carried out with a photoinitiator as described in WO2019 / 097021 and in the absence of other external (photo)initiators

[0154] In particular, in the photopolymerization step at least one charge is reacted with at least one compound of formula (I) as described above and / or at least one metal complex of the compound of formula (I) as described above, in the presence of at least one free or immobilized photoinitiator on a charge and light irradiation.

[0155] In particular, when the complexation step of the compound of formula (I) is carried out prior to the photopolymerization step, in the photopolymerization step the compound obtained in the complexation step is reacted in the presence of the charge and the photoinitiator or the compound obtained in the complexation step is reacted with a compound of formula (I) in the presence of the charge and the photoinitiator.

[0156] The photopolymerization step can also be carried out in the presence of at least one additional monomer from the acrylic family, this monomer being different from the compound of formula (I) and / or the metal complex of the compound of formula (I). For example, this additional monomer is di(trimethylolpropane)tetraacrylate, hereinafter referred to as "DTMPTA". Other monomers such as di(trimethylolpropane)tetraacrylate and odecafluoroheptyl acrylate can also be used to adjust the textural and chemical properties of the hybrid materials.

[0157] At the end of the photopolymerization step, a hybrid material is obtained comprising a porous or non-porous filler linked to a polymer, this polymer being formed in particular from at least one functionalized bipyridine derivative of formula (I) as described above and / or from at least one metal complex of the derivative of formula (I).

[0158] In particular, the polymer of the hybrid material may be a branched or crosslinked polymer formed from at least one compound of formula (I) as described above or obtained by the process described above.

[0159] Advantageously, the polymer of the hybrid material obtained from the 2,2'-bipyridine compound functionalized with acrylic functions according to the invention is three-dimensional.

[0160] Advantageously, the polymer forms a shell around the filler.

[0161] The polymer of the hybrid material may also be a branched or crosslinked polymer comprising or consisting of at least one compound of formula (I) as described above and / or at least one metal complex of the compound of formula (I). In particular, the polymer of the hybrid material may be a homopolymer obtainable by the photopolymerization of the compound of formula (I) or a homopolymer obtainable by the photopolymerization of the metal complex of the compound of formula (I). The polymer of the hybrid material may also be a copolymer obtainable by the photopolymerization of a compound of formula (I) with a metal complex of the compound of formula (I).

[0162] According to one aspect of the invention, a polymer of the hybrid material may be a copolymer capable of being obtained by photopolymerization of a compound of formula (I) and / or photopolymerization of a metal complex of the compound of formula (I) with an additional monomer of the acrylic family.

[0163] In other words, the polymer of the hybrid material comprising or consisting of at least one compound of formula (I) and / or at least one metal complex of the compound of formula (I), as described above, can be obtained by a process comprising a photopolymerization step in which said at least one compound of formula (I) or metal complex is reacted with at least one photoinitiator under light irradiation. The photoinitiator may be immobilized or unimmobilized on a charge.

[0164] In other words, hybrid materials include a porous or non-porous filler bonded to three-dimensional branched or crosslinked polymers formed from at least one compound of formula (I) and / or at least one metal complex of the compound of formula (I), the metal complex comprising a compound of formula (I) and at least one transition metal.

[0165] The general and specific aspects of the invention described above apply equally to compounds of formula (I), to their preparation process and to the polymers comprising them.

[0166] < Complexation of the hybrid material after photopolymerization >

[0167] In particular, the process for preparing a hybrid material may include, after the photopolymerization step, a complexation step in which the hybrid material obtained in the photopolymerization step is reacted with at least one transition metal. This embodiment is particularly advantageous when the transition metal is rhenium.

[0168] Thus, in a preferred embodiment of the invention, in the complexation step subsequent to the photopolymerization step, the hybrid material obtained in the photopolymerization step is reacted with rhenium, in particular pentacarbonylchlororhenium(l) of formula Re(CO)5Cl.

[0169] A preferred method for preparing the hybrid material includes:

[0170] An optional step of grafting the charge with the photoinitiator; A complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal, preferably ruthenium, this step being carried out prior to the photopolymerization step;

[0171] A photopolymerization step in which the compound obtained in the complexation step is reacted with a compound of formula (I) in the presence of the filler and the photoinitiator; and

[0172] A step of complexing the hybrid material obtained in the photopolymerization step with at least one transition metal, preferably rhenium, this step being carried out after the photopolymerization step.

[0173] Preferably, in said process for preparing a hybrid material, at least one of the following conditions is met:

[0174] - the charge is previously linked to the silane-type photoinitiator;

[0175] - the photoinitiator content is 0.1 to 2% by weight relative to the weight of the compound of formula (I) and / or the metal complex of the compound of formula (I) as described above;

[0176] - the photoinitiator content is 6% to 10% by weight relative to the weight of the charge;

[0177] - the photopolymerization step is carried out in solution in the presence of an organic solvent, preferably acetonitrile;

[0178] - light irradiation is monochromatic or polychromatic irradiation;

[0179] - the photopolymerization step is carried out, in addition, in the presence of at least one additional (co)monomer from the acrylic family;

[0180] - the photopolymerization step is carried out, in addition, in the presence of at least one metallic complex as described above.

[0181] The invention also relates to a method for preparing a hybrid material comprising at least one transition metal, comprising:

[0182] - the reaction of a compound of formula (I) as described above with a transition metal; or

[0183] - the reaction of a polymer as described above with a transition metal; or

[0184] - the reaction of a hybrid material as described above with a transition metal, said transition metal being, preferably chosen from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, more preferably ruthenium, rhenium or iridium, more preferably ruthenium or rhenium.

[0185] < atériau h flange. > The invention also relates to a hybrid material that can be obtained by the process described above.

[0186] The invention also relates to a hybrid material further comprising at least one transition metal, preferably two transition metals.

[0187] Advantageously, said transition metal is chosen from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium, rhenium or iridium, more preferably ruthenium or rhenium.

[0188] An advantageous hybrid material according to the invention is one in which at least one of the following conditions is met:

[0189] - the hybrid material comprises at least two metals;

[0190] - the polymer is as defined above;

[0191] - the charge is a zeolite;

[0192] - the transition metal(s) are Ru(ll) and / or Re(ll).

[0193] A preferred hybrid material according to the invention is one in which at least one of the following conditions is met:

[0194] - the content of the filler is between 10 and 200% by weight relative to the compound of formula (I);

[0195] - the polymer content is between 10 and 200% by weight relative to the hybrid material;

[0196] - the mass ratio of filler to polymer is between 4 and 0.1.

[0197] The general and particular aspects of the invention described above apply equally to compounds of formula (I), to metallic complexes comprising them, to polymers based on compounds of formula (I), to hybrid materials comprising a porous or non-porous filler linked to said polymer, to hybrid materials comprising at least one transition metal and also to their preparation processes.

[0198] According to one aspect, the invention also relates to the use of a hybrid material as described above, in particular a hybrid material comprising at least one transition metal, in at least one of the following applications:

[0199] - as a ligand;

[0200] - as a probe or imaging agent; - as a catalyst, preferably for the reduction of CO2, preferably photocatalyzed or electrocatalyzed;

[0201] - as a photocatalyst, preferably in the photoreduction of CO2 or the photocatalyzed decomposition of water; - as a photosensitizer, particularly in solar cells;

[0202] - as a component of metal-based medicines;

[0203] - as an intermediate in the synthesis of supramolecular molecules;

[0204] - as a basic component of an item obtained by 3D printing;

[0205] - as a complexing compound for the degradation of pollutants. The invention is illustrated in a non-limiting way by the following examples.

[0206] EXAMPLES

[0207] Example 1: Synthesis of the compound [2,2'-bipyridine]-4,4'-diyldiacrylate

[0208] The compound [2,2'-bipyridine]-4,4'-diyldiacrylate was synthesized in one step from [2,2'-Bipyridine]-4,4'-diol (commercially available).

[0209] A solution of [2,2'-Bipyridine]-4,4'-diol (1 equivalent) in chloroform, acryolyl chloride (7 equivalents, 2 mL, 22.5 mmol), and triethylamine (6 equivalents, 3 mL, 19.14 mmol) at a pH between 8.0 and 9.0 is heated at 60°C under reflux for 24 h. The organic phase is then extracted from the mixture using chloroform and dried by adding MgSCU. The extracted organic phases are combined, and the chloroform is evaporated under reduced pressure (P = 100 mbar, T = 50 °C). The crude product is purified on a silica gel chromatography column (VWR chemicals, CAS: 7631-86-9, 60.08 g / mol, SiO2) using a dichloromethane:methanol (98:2) mixture as the eluent. The pure final product is obtained with a yield of 42% in the form of a white solid with a purity of 99%.

[0210] 1 H NMR (500 MHz, DMSO-d6) 5: 8.79 (d, 2H, J = 5.4 Hz), 8.28 (d, 2H, J = 1.95 Hz), 7.46 (dd, 2H, Ji = 5.2 Hz, J2 = 2.15 Hz), 6.66 (d, 2H, J = 17.21 Hz), 6.5 (dd, 2H, Ji = 17.21 Hz, J2 = 10.4 Hz), 6.28 (d, 2H, J = 10.45 Hz).

[0211] Example 2: Synthesis of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate

[0212] The compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate was synthesized in one step from 2,2'-Bipyridine-4,4'-dimethanol.

[0213] A solution of [2,2'-bipyridine]-4,4'-diylbis(methylene)-dimethanol (15 g, 69 mmol, 1 equivalent) in chloroform, triethylamine (62 mL, 416 mmol, 6 equivalents), and acryolyl chloride (40 mL, 486 mmol, 7 equivalents) at a pH between 8.0 and 9.0 is stirred at 0°C for 30 min and then for 18 h at room temperature under reflux. The organic phase is then extracted from the mixture using chloroform and dried by adding MgSCU. The extracted organic phases are combined, and the chloroform is evaporated under reduced pressure (P = 100 mbar, T = 50 °C). The crude product obtained is purified on a silica gel chromatography column (VWR chemicals, CAS: 7631-86-9, 60.08 g / mol, SiO2) using a dichloromethane:methanol (98:2) mixture as the eluent. The final pure product (9.5 g), whose formula is given below, is obtained in a yield of 43% as a white solid with a purity greater than 99%.

[0214] 1 H NMR (500 MHz, DMSO-d6) 5: 8.73 (d, 2H, J = 4.91 Hz), 8.42 (s, 2H), 7.5 (d, 2H, J = 4.66 Hz), 6.48 (d, 2H, J = 17.6 Hz), Jidd = 17.6.41 17.15 Hz, J2=10.3 Hz), 6.08 (d, 2H, J = 10.4 Hz), 5.39 (s, 4H). 13 C NMR (125 MHz, DMSO-d6) 5 : 166.15 (C=O) ; 156.05 ; 150.50 ; 147.41 ; 133.50 ; 128.78 ;

[0215] 123.36 ; 119.48 ; 65.09 (CH2).

[0216] HRMS (ESI+): calculated from [M+H] + = 325.1 1 ; found =325.1,186.

[0217] Example 3: Synthesis of the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)Re(CO)3Cl. A solution of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate obtained in Example 2 (1 equivalent, 92 mg, 0.25 mmol), in toluene and pentacarbonylchlororhenium(l) (Re(CO)5Cl, 1 equivalent, 81 mg, 0.25 mmol), is heated at 110°C under reflux overnight. The toluene is then evaporated. (P = 50 mbar, T = 55°C) After evaporation, a yellow crude product is dried in an oven at 60°C. The pure final product, ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)Re(CO)sCl, whose formula is given below, is obtained with a yield of 82% and a purity greater than 99%.

[0218]

[0219] The results show that the compound obtained in example 2 is able to complex rhenium despite the steric hindrance induced by the presence of two acrylic functions in positions 4 and 4' of the bipyridinic ring. 1 H NMR (500 MHz, DMSO-d6) 5: 9.28 (d, 2H, J = 5.78 Hz), 8.22 (s, 2H), 7.63 (d, 2H, J = 5.6 Hz), 6.57 (d, 2H, J = 17.34 Hz), 6.26 (dd, 2H, Ji = 17.42 Hz, J2=10.59 Hz), 6.03 (d, 2H, J = 10.48 Hz), 5.44 (s, 4H).

[0220] 13 C NMR (125 MHz, DMSO-d6) 5: 166.04 (C=O), 155.96; 154.04; 150.94; 133.85; 129.84; 129.15; 128.58; 126.67; 126.26; 123.33; 64.60 (CH2). HRMS (ES l+): calculated from [M+H] + = 653.02; found = 653.0098

[0221] Example 4: Synthesis of the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2

[0222] A solution of [2,2'-bipyridine]-4,4'-diylbis(methylene)diacrylate obtained in Example 2 (2 equivalents, 183 mg, 0.52 mmol) in ethanol and cis-dichlorobis(bipyridine)ruthenium(II) (Ru(bpy)2Cl2, 1 equivalent, 130 mg, 0.26 mmol) is heated under reflux at 78°C. After centrifugation, a crude product is dried in an oven at 60°C. The final pure product, the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene)diacrylate)(bipyridine)2RuCl2, whose formula is given below, is obtained as a red solid with a yield of 42% and a purity greater than 99%.

[0223] The results show that the compound obtained in example 2 is able to complex with ruthenium despite the steric hindrance induced by the presence of two acrylic functions in positions 4 and 4' of the bipyridinic ring. 1 H NMR (500 MHz, DMSO-d6) 5: 8.90 (d, 6H, J = 8.87 Hz), 8.21 (t, 4H, J = 7.5 Hz), 7.79 (d, 2H, J = 5.88 Hz), 7.76, J 4 (d = 2 Hz), H 2H, J = 5.22 Hz), 7.56 (m, 6H), 6.49 (d, 2H, J = 17.34 Hz), 6.34 (dd, 2H, Ji = 17.11 Hz, J2=10.29 Hz), 6.10 (d, 4 Hz), 2.5 s, J = .

[0224] 13 C NMR (125 MHz, DMSO-d6) 5: 166 (C=O) ; 157.47 ; 157.46 ; 157.23 ; 152.27 ; 152.19 ; 152.11 ; 148.23 ; 138.92 ; 138.88 ; 133.85 ; 128.84 ; 128.55 ; 126.75 ; 125.46 ; 123.53 ; 64.42

[0225] (CH2).

[0226] HRMS (ES+): calculated from [M / 2] = 369.0745, found =369.0769.

[0227] Example 5: Synthesis and Characterization of the ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) Hybrid Material. The hybrid material consisting of a zeolite (Faujasite X), hereinafter referred to as "ZX", bonded to a poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) was obtained by the photopolymerization of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound obtained in Example 2. The polymerization yield of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound, determined according to the procedure described in Example 8 below, is 60% of the zeolite.

[0228] A nanoparticulate zeolite X of the Faujasite type is first prepared according to the procedure cited in the article M. El-Roz et al., ACS Appl. Mater. Interfaces, 2018, 10, 28702-28708, (Supporting Information, section I, S3-S4, “sample ZX”) from a suspension of molar composition: 10 SiC>2 : 1 ,1 Al2O3 : 9 Na2U : 122 H2O.

[0229] Zeolite grafting

[0230] The zeolite thus prepared was then linked to silane-type photoinitiators.

[0231] The dried zeolite (1 g, 1 equivalent) is dehydrated at 150°C under constant stirring. A silane-type photoinitiator, SPI-1 (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-1-one, 0.275 mmol, 1 equivalent), described in application WO2019 / 097021, is dissolved in ethanol (1 mL). This solution is dispersed over the zeolite and maintained under stirring at 120°C for 30 min. The resulting white solid, corresponding to the zeolite bound to the photoinitiators, is washed and dispersed three times in an acetonitrile / water (v / v) mixture and then in water, and is subsequently dried at 50°C for 12 h to remove residual traces of solvents.

[0232] The use of ethanol is optional and aims to improve the dispersion of the silane-type photoinitiator on the zeolite while evaporating very quickly. The washing step, also optional, was performed solely to estimate the exact amount of photoinitiator grafted.

[0233] Photopollution of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate

[0234] The hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) was then prepared by photopolymerization.

[0235] The previously prepared zeolite (50 mg) was dispersed in acetonitrile (20 mL) by sonication. The compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (20 mg) obtained in Example 2 was added to the solution. The resulting mixture was stirred and bubbling with argon for 15 min. The mixture was then subjected to monochromatic irradiation for 15 min using a 365 nm LED lamp with an irradiance of 0.3 W / cm². 2 while maintaining agitation and bubbling. The resulting precipitate was collected after a centrifugation step. Excess [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer was removed by washing with acetonitrile. A water wash was then performed to remove residual traces of solvent. The resulting solid compound was then dried at 50°C for 12 hours. A monitoring of the photopolymerization kinetics of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate was carried out from a suspension of the reaction mixture in acetonitrile by measuring the absorbance of the reaction mixture at 365 nm using a Cray 4000 UV-visible spectrophotometer.

[0236] The polymerization evolution of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate is shown in Figure 1, in which:

[0237] - Curve (a) corresponds to the percentage of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate polymerized over time during the synthesis of the hybrid material in the example

[0238] 5;

[0239] - Curve (b) corresponds to the percentage of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate polymerized over time during the synthesis of the hybrid material in the example

[0240] 6 below.

[0241] This result (figure 1 curve (a)) confirms that the monomeric compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate of example 2 is capable of polymerizing efficiently in the presence of a filler.

[0242] Characterization of the crystallinity and purity of the hybrid material

[0243] The crystallinity and purity of the ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material obtained were characterized by powder X-ray diffraction (PXRD) analysis and by Fourier transform infrared (FTIR) spectroscopy.

[0244] PXRD analysis was performed using a PANalytical X'Pert Pro diffractometer with a mean CuKa wavelength of 1.5418 Å. Refinements of the Rietveld method were then performed using JANA2006 software on the PXRD data recorded on a Bruker D8-vario1 diffractometer equipped with a primary germanium Johansson monochromator (111) with a wavelength of Ka1 = 1.5406 Å and a LynxEye detector. PXRD patterns were recorded at room temperature between 3 and 120°C (20°F) with a step size of approximately 0.014° (20°F). Variable diverging slits with a constant illuminated sample length of 6 mm were used. Phase identifications were performed using the PANalytical HighScore Plus program. The powder X-ray diffraction (PXRD) spectrum of the resulting ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material is shown in Figure 2, in which:

[0245] - curve (a) is the diffraction spectrum of pure zeolite;

[0246] - curve (b) is the diffraction spectrum of the zeolite grafted with the SPI-1 photoinitiator;

[0247] - curve (c) is the diffraction spectrum of the zeolite grafted with the photoinitiator SPI-1 after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; and - curve (d) is the diffraction spectrum of the zeolite grafted with the photoinitiator SPI-1 after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and di(trimethylolpropane) tetraacrylate (from example 6 below).

[0248] For FTIR analysis, the product obtained in powder form was pressed to approximately 10 7 Pa / cm 2 , inserted into a self-supporting disc (area of ​​2 cm²) 2 (approximately 20 mg) and placed in a Nicolet 6700 IR spectrometer equipped with a DTGS (Deuterated Triglycine Sulfate) detector and an expandable KBr beam splitter. The spectrometer was recorded from 128 scans performed from 400 to 5500 cm⁻¹ -1 at a resolution of 4 cm 1 .

[0249] The FTIR spectra are shown in Figure 3, in which:

[0250] - curve (a) represents the FTIR spectrum of pure zeolite;

[0251] - curve (b) represents the FTIR spectrum of the zeolite grafted with the SPI-1 photoinitiator;

[0252] - Curve (c) represents the FTIR spectrum of the zeolite grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; and

[0253] - curve (d) represents the FTIR spectrum of the zeolite grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and di(trimethylolpropane) tetraacrylate (from example 6 below).

[0254] The results obtained confirm the production of a pure solid and the preservation of the zeolite's crystalline structure. The results also show that photopolymerization of the bipyridine derivative from Example 2 onto the zeolite does not affect the filler structure.

[0255] Example 6: Synthesis of the hybrid copolymer material of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and DMPTA on a zeolite

[0256] The hybrid material consisting of a zeolite (Faujasite X), hereinafter referred to as "ZX", bonded to a copolymer of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and di(trimethylolpropane) tetraacrylate, hereinafter referred to as "DTMPTA", was obtained by the photopolymerization of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound obtained in Example 2 and DTMPTA. The polymerization yield of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound, determined according to the procedure described in Example 8 below, is 85%.

[0257] The preparation and grafting of a nanoparticulate Faujasite-type zeolite X were carried out as in Example 5. During the photopolymerization step, the procedure described in Example 5 was performed, this time adding the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (20 mg) and DTMPTA (100 mg) to the zeolite solution. The photopolymerization yield of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and the bipyridine content in the hybrid material were calculated as in Example 5.

[0258] Kinetics of oolvmerization

[0259] Monitoring of the photopolymerization kinetics of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate was carried out as in example 5 from a suspension of the reaction mixture in acetonitrile by measuring the absorbance of the reaction mixture at 365 nm.

[0260] The evolution of the polymerization of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate shown in Figure 1 curve (b) shows that the monomer compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate of Example 2 is able to polymerize efficiently in the presence of an acrylate comonomer.

[0261] Crystallinity and purity of the hybrid material

[0262] The crystallinity and purity of the resulting ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; DTMPTA) hybrid material were characterized as in Example 5. The powder X-ray diffraction pattern (Fig. 2, curve (d)) and the FTIR pattern (Fig. 3, curve (d)) of the hybrid material confirm the formation of a pure solid and the preservation of the zeolite's crystalline structure. The results show that photopolymerization of the zeolite in the presence of an acrylic comonomer (DTMPTA in this example) does not affect the filler structure.

[0263] Example 7: Synthesis of a hybrid material of a copolymer of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 on a zeolite.

[0264] The hybrid material consisting of a zeolite (Faujasite X), hereinafter referred to as "ZX", linked to a copolymer of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 was obtained by the photopolymerization of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate of Example 2 and the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 of Example 4. The yield of the polymerization of the complexed and uncomplexed [2,2'-bipyridine] derivatives, determined according to the procedure described in Example 8 below, is 40%.

[0265] The preparation and grafting of a nanoparticulate Faujasite-type zeolite X were carried out as in Example 5. During the photopolymerization step, the procedure described in Example 5 was performed, this time adding the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (20 mg) and the complex [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 (5 mg) to the zeolite solution. Example 8: Determination of the photopolymerization yield of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and / or [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2

[0266] The photopolymerization yield and the content of polymerized bipyridines (complexed and uncomplexed with Ru) on the zeolite were measured by UV-visible spectroscopy analysis of the supernatant solution. The conversion yield was calculated using the 285 nm intensity of the [2,2'-bipyridine]-4,4'-diylbis(methylene) characteristic band associated with TT-TT* transitions centered in the heterocyclic ligands before (l0) and after (I) photopolymerization from the equation: photopolymerization yield (%) = x 100.

[0267] The content of polymerized bipyridines in the final hybrid material was also determined from the photopolymerization yield. The number of moles of polymerized bipyridines is determined by knowing the initial amount of bipyridine used and the remaining unpolymerized amount.

[0268] The yields thus calculated of the photopolymerization of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and / or of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 during the preparation of the hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) of example 5, of the hybrid material of example 6 and of the hybrid material of example 7 are reported in Table (1).

[0269] These results show that the bipyridine derivatives synthesized in examples 2 and 4 are capable of polymerizing.

[0270] The results show that the presence of DTMPTA does not have an adverse impact on the photopolymerization yield of the bipyridine derivative and the final bipyridine content in the hybrid material when the photopolymerization step was carried out in the presence of DTMPTA.

[0271] Example 9: Synthesis of the hybrid material ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate] Re(CO)3Cl) by complexation of the hybrid material of Example 5 with rhenium. A solution of the hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate), prepared in Example 5 (100 mg, 1 equivalent), in toluene (6 mL) and pentacarbonylchlororhenium(l) (Re(CO)5Cl, 104 mg, 1.1 equivalents) is heated at 110°C under reflux overnight. The toluene is then evaporated. The resulting product is washed to remove excess Re(CO)5Cl complexes and then dried in an oven at 50°C.

[0272] The pure final product, ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl), is obtained with a complexation yield of 50% and an Re content of 0.3 mmol / g, determined according to the procedure described in Example 13 below.

[0273] Accessibility of zeolite pores

[0274] The accessibility of the zeolite pores before and after the photopolymerization and complexation steps was determined by the N2 adsorption / desorption isotherm and the CO2 absorption isotherm on the ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl hybrid material). These analyses allow us to assess the impact of the polymer's presence on pore accessibility. The pure zeolite prepared in Example 5 and the poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl polymer) prepared in Example 12 below were used as controls.

[0275] The adsorption / desorption isotherm of N2 on the zeolite is shown in Figure 4, in which:

[0276] - curve (a) represents the absorption / desorption isotherm of N2 on pure zeolite (from example 5);

[0277] - Curve (b) represents the absorption / desorption isotherm of N2 on the hybrid material ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl); and

[0278] - curve (c) represents the absorption / desorption isotherm of N2 on poly([[2,2'- bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl) (from example 12 below).

[0279] The adsorption isotherm of CC^ on zeolite is shown in Figure 5, in which:

[0280] - curve (a) represents the absorption / desorption isotherm of CO2 on pure zeolite (from example 5);

[0281] - Curve (b) represents the CO2 absorption / desorption isotherm on the hybrid material ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl); and

[0282] - curve (c) represents the absorption / desorption isotherm of CO2 on poly([[2,2'- bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl) (from example 12 below).

[0283] The results show that the zeolite porosity remains significantly accessible even when the zeolite particles are coated with poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl). Therefore, the presence of the polymer on the porous filler does not affect the accessibility of the filler's porosity.

[0284] Example 10: Complexation of the hybrid material of Example 7 with rhenium. A solution of the material of Example 7 (100 mg, 1 equivalent) in toluene (6 mL) and excess pentacarbonylchlororhenium(l) (Re(CO)5Cl, 104 mg, 1.1 equivalents) is heated at 110°C under reflux overnight. The toluene is then evaporated. The resulting product is washed to remove excess Re(CO)5Cl complexes and then dried in an oven at 50°C.

[0285] The pure final product is obtained with a complexation yield of 67% and an Re content of 0.2 mmol / g, determined according to the procedure described in Example 13 below.

[0286] The complex thus formed comprises two transition metals: rhenium and ruthenium. The hybrid material in Example 10 therefore comprises two transition metals: rhenium and ruthenium.

[0287] Example 11 (comparative): Synthesis of a filler-free polymer: poly([2,2'-bipyridine]- 4,4'-diylbis(methylene) diacrylate)

[0288] Preparation of poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)

[0289] A solution of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (20 mg) obtained in Example 2 in acetonitrile (20 mL) and the silane-type photoinitiator SPI-1 (1 wt% by weight relative to the amount of monomer) was stirred and bubbling under argon for 15 min. The solution was then subjected to monochromatic irradiation for 15 min using a 365 nm LED lamp with an irradiance of 0.3 W / cm² 3 while maintaining agitation and boiling. The resulting precipitate was collected after a centrifugation step. Excess [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer was removed by washing with acetonitrile. A water wash was then performed to remove residual traces of solvent. The resulting solid compound was then dried at 50°C for 12 h before being characterized.

[0290] Photopollution yield of the monomer [2,2'-bipyridinel-4,4'-diylbis(methylene)

[0291] The photopolymerization yield of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer was determined as in Example 8. The polymerization yield is 75%.

[0292] The results show that the photopolymerization yields of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer in the presence and absence of filler are of the same order of magnitude. Thus, immobilization of the polymer on the filler during photopolymerization does not significantly affect the photopolymerization yield.

[0293] Example 12 (comparative): Synthesis of poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) A solution of poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) (0.048 mmol) obtained in Example 11 in toluene and pentacarbonylchlororhenium(l) (Re(CO)5Cl, in excess) (0.058 mmol) is heated at 110°C under reflux overnight. The toluene is then evaporated. The product obtained is washed to remove excess Re(CO)5Cl complexes and then dried. The yield of the complexation reaction, determined according to the procedure described in Example 13 below, is 50%.

[0294] Example 13: Complexation reaction yield and rhenium content

[0295] The rhenium content in each final product obtained in examples 9, 10 and 12 is determined by FTIR spectroscopy by considering the band corresponding to the C=O bond vibration at 2025cm -1 .

[0296] Each product obtained in powder form was pressed to approximately 10 7 Pa / cm 2 , then inserted into a self-supporting disc (area of ​​2 cm²) 2 (approximately 20 mg) and then placed in an IR cell of a Nicolet 6700 IR spectrometer equipped with a DTGS (Deuterated Triglycine Sulfate) detector and an expandable KBr beam splitter. In the IR cell, the powder was activated by heat treatment. Each spectrum was recorded from 128 scans performed at 400 to 5500 cm⁻¹ -1 at a resolution of 4 cm -1 .

[0297] The yield of the complexation reaction was determined using the previously calculated bipyridine and rhenium contents. The results (content and yield) are reported in Table 2 below.

[0298] The results show that the hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) according to the invention prepared in Example 5 efficiently forms a complex with rhenium.

[0299] The results also show that the yield of rhenium complexation with poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) is identical to that obtained when the polymer is immobilized on the zeolite (Examples 9 and 12). Therefore, the presence of the filler does not affect the efficiency of the complexation of bipyridine derivatives.

[0300] Furthermore, the results show that it is possible to obtain a hybrid material comprising two different transition metals from the bipyridine derivative prepared in Example 2 (Example 10).

[0301] Example 14: Use of hybrid materials as catalysts in the photocatalytic reduction of CO2. The photocatalytic performance of the hybrid materials synthesized in Examples 9 and 10 was determined during the photocatalytic reduction of CO2. The compound obtained in Example 12, which does not contain a filler, was used for comparison.

[0302] The reaction was carried out at room temperature in a batch reactor as described in I. Telegeiev et al., Anal. Chem. 2018, 90, 24, 14586-14592. All in situ IR spectroscopy measurements were monitored in real time with a temporal resolution of 5 min per spectrum using a Nicolet 6700 IR spectrometer (Thermo Fisher 14 Scientific) equipped with an MCT detector. A 405 nm LED (Hamamatsu) was used as the light source. The hybrid material, in the form of a complex synthesized in Example 9 (3 mg) or Example 10 (3 mg), or the reference compound synthesized in Example 12 (3 mg), was dispersed in a dimethylformamide / H2O mixture (10 / 1.8 mL). CO2 bubbles were introduced into the solution for 1 h at a flow rate of 8 mL / min. Triethanolamine (TEOA, 0.12 M) was then introduced as an electron donor (220 mg in 1 mL) while maintaining CO2 bubbling for 15 min.The photocatalyzed reduction of CO2 was performed three times for each hybrid or reference material used. The error values ​​obtained are less than 10%, demonstrating high reproducibility of the reaction.

[0303] By measuring the absorbance of each reaction mixture at 405 nm, the kinetics of the photocatalytic reduction of CO2 were determined. The evolution of the amount of CO2 produced over time is shown in Figure 6, in which:

[0304] - curve (a) represents the reduction of CO2 photocatalyzed by poly([[2,2'-bipyridine]-4,4'- diylbis(methylene) diacrylate]Re(CO)sCl) (from example 12);

[0305] - curve (b) represents the reduction of CO2 photocatalyzed by the hybrid material ZX- poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl) (from example 9); and

[0306] - curve (c) represents the reduction of CO2 photocatalyzed by the hybrid material comprising rhenium and ruthenium (from example 10).

[0307] The stability of the photocatalytic activity of the hybrid material ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl) (from Example 9) as a catalyst is shown in Figure 7.

[0308] The results show that the presence of a microporous support (zeolite in this example) improves photocatalytic performance. The results also show that the photocatalytic performance of the hybrid materials according to the invention is stable over time.

[0309] Example 15: Synthesis of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl hybrid material. The hybrid material consisting of a MOF (UiO-66), hereinafter referred to as "MOF," bonded to a poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) was obtained by the photopolymerization of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound. The polymerization yield of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate compound, determined according to the procedure described in Example 8 below, is between 40 and 50%. MOF Preparation

[0310] The UiO-66 nanoparticles are first prepared according to the procedure described in the article Jrad, A. et al., Structural engineering of Zr-based metal-organic framework catalysts for optimized biofuel additives production. Chemical Engineering Journal 382, ​​122793 (2020). MOF grafting

[0311] The resulting powder (100 g) is dehydrated at 200°C under constant stirring and then cooled to 120°C. A silane-type photoinitiator, SPI-1 (2,2-dimethyl-1-phenyl-5-(triethyloxysilyl)pentan-l one, 0.275 mmol, 1 equivalent), described in application WO2019 / 097021, is dissolved in ethanol (1 mL). This solution is dispersed onto the MOF and maintained under stirring at 120°C for 30 min.

[0312] The resulting solid, corresponding to the MOF linked to the photoinitiators, is washed and dispersed three times in an acetonitrile / water mixture (50:50 v / v) then in water and is then dried at 60°C for 12h to remove residual traces of solvents.

[0313] The use of ethanol is optional and aims to improve the dispersion of the silane-type photoinitiator on the MOF while evaporating very quickly. The optional washing step was performed solely to estimate the exact amount of photoinitiator grafted.

[0314] Photopolymerization of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate

[0315] The hybrid MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) material was then prepared by photopolymerization.

[0316] Specifically, the previously prepared MOF (50 mg) was dispersed in acetonitrile (20 mL) by sonication. The compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (200 mg) was added to the solution in a sealed reactor. The resulting mixture was stirred and bubbling with argon for 15 min. The mixture was then subjected to monochromatic irradiation for 15 min using a 365 nm LED lamp with an irradiance of 0.3 W / cm². 2 while maintaining agitation and bubbling. The resulting precipitate was collected after a centrifugation step. Excess [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer was removed by washing with acetonitrile. A water wash was then performed to remove residual traces of solvent. The resulting solid compound, corresponding to MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate), was then dried at 50°C for 12 h. of the material obtained, MOF-poly([2,2'-bipyridine]-4,4'- with rhenium

[0317] A solution containing the solid compound and pentacarbonylchlororhenium(l) (Re(CO)5Cl) in toluene is then heated at 110°C under reflux overnight. The toluene is then evaporated. The resulting product is washed to remove excess Re(CO)5Cl complexes (1.5 relative to bpy) and then dried.

[0318] The pure final product, MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl), is obtained with a complexation yield of 70% and a Re content of 1 mmol / g, determined according to the procedure described in Example 13 above. Characterization of the crystallinity and purity of the hybrid materials (containing or not containing rhenium) obtained

[0319] The crystallinity and purity of the MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material complexed or not complexed with rhenium were characterized as in Example 5, namely by powder X-ray diffraction (PXRD) analysis and by Fourier transform infrared (FTIR) spectroscopy.

[0320] The powder X-ray diffraction (PXRD) spectrum of the obtained MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material and the rhenium-containing MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene)-diacrylate]Re(CO)3Cl) hybrid material are shown in Figure 8, in which:

[0321] - curve (a) is the diffraction spectrum of the pure MOF;

[0322] - curve (b) is the diffraction spectrum of the MOF grafted with the SP 1-1 photoinitiator;

[0323] - curve (c) is the diffraction spectrum of the MOF grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; and

[0324] - curve (d) is the diffraction spectrum of the MOF grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and after complexation with rhenium.

[0325] The FTIR spectra are shown in Figure 9, in which:

[0326] - curve (a) represents the FTIR spectrum of the pure MOF;

[0327] - curve (b) represents the FTIR spectrum of the MOF grafted with the SPI-1 photoinitiator;

[0328] - Curve (c) represents the FTIR spectrum of the MOF grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; and

[0329] - curve (d) represents the FTIR spectrum of the MOF grafted with the SPI-1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and after complexation with rhenium.

[0330] The results obtained confirm the formation of a pure solid and the preservation of the MOF's crystalline structure. The results also show that photopolymerization of the bipyridine derivative from Example 2 onto the MOF does not affect the filler structure. These results further demonstrate the successful complexation of the MOF-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material with rhenium.

[0331] MOF pore accessibility

[0332] The accessibility of the MOF pores before and after the photopolymerization and complexation steps was determined as in Example 9, namely by the N2 adsorption / desorption isotherm and by the CO2 absorption isotherm on the rhenium-containing hybrid material, MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl).

[0333] In particular, nitrogen adsorption / desorption analyses were performed on a Model ASAP 2020. After degassing at 200°C under vacuum for 12 hours, the samples were cooled and nitrogen adsorption was carried out. Specific surface areas were determined using the BET method. The total pore volume corresponds to the total volume adsorbed at P / P° = 0.99. The t-plot method was used to distinguish micropores from mesopores. The results are reported in Table 3 below:

[0334] The CO2 adsorption isotherm on the MOF is shown in Figure 10, in which:

[0335] - curve (a) represents the absorption / desorption isotherm of CO2 on the pure MOF;

[0336] - curve (b) represents the absorption / desorption isotherm of CO2 on the hybrid material MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl).

[0337] The adsorption isotherm of N2 on the MOF is shown in Figure 11, in which:

[0338] - curve (a) represents the absorption / desorption isotherm of N2 on the pure MOF;

[0339] - curve (b) represents the absorption / desorption isotherm of N2 on the MOF-poly hybrid material ([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl).

[0340] The results show that the MOF porosity remains significantly accessible even when the MOF particles are coated with poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl). Specifically, approximately 50% of the pores in the MOF of the hybrid MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) material remain accessible. Therefore, the presence of the polymer on the porous filler does not significantly affect the accessibility of the filler's porosity.

[0341] Example 16: Use of MOF-containing hybrid material as a photocatalyst in CO2 reduction

[0342] The photocatalytic performance of the hybrid material including rhenium synthesized in Example 15 was determined during the photocatalytic reduction of CO2.

[0343] The reaction was carried out under the same operating conditions as in Example 14, and the in situ IR spectroscopy measurements were performed as in Example 14. In particular, the rhenium hybrid material in complex form synthesized in Example 15 (5 mg) was dispersed in a dimethylformamide / FhO₂ mixture (10 / 1.8 mL). CO₂ bubbles were introduced into the solution for 1 h at a flow rate of 8 mL / min. Triethanolamine (TEOA, 0.12 M) was then introduced as an electron donor (220 mg in 1 mL) while maintaining CO₂ bubbling for 15 min. Following the reaction, the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl) was recovered by a simple filtration step.

[0344] A solution containing the homogeneous catalyst Re(2,2'-bipyridine)(CO)3Cl) at 5x10 -4 M in dimethylformamide (DMF) was used as a reference. The reference catalyst could not be recovered after the reaction by a simple filtration step.

[0345] The suspension of the hybrid material comprising rhenium from Example 15 in DMF and the reference solution of Re(2,2'-bipyridine)(CO)3Cl) in DMF include a comparable number of catalytic centers allowing for a semi-quantitative comparison, although the actual activity of the hybrid material comprising rhenium from Example 15 may be underestimated.

[0346] The photocatalyzed reduction of CO2 was performed twice for each catalyst used. The error values ​​obtained ranged from 10 to 20%, demonstrating high reproducibility of the reaction.

[0347] By measuring the absorbance of each reaction mixture at 405 nm, the kinetics of the photocatalytic reduction of CO2 were determined. The evolution of the amount of CO2 produced over time is shown in Figure 12, in which:

[0348] - curve (a) represents the reduction of CO2 photocatalyzed by the homogeneous catalyst Re(2,2'-bipyridine)(CO)3Cl) used as a reference;

[0349] - curve (b) represents the reduction of CO2 photocatalyzed by the hybrid material MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl synthesized in example 15.

[0350] Furthermore, the rotation frequency (TOF, also called "turnover frequency" in English) and the rotation number (TON, also called "turnover number" in English) of the two catalysts were determined when the reaction mixture was irradiated by a sunlight simulator using the following formulas:

[0351] With n in moles and t in hours.

[0352] The results are shown in Figure 13, in which:

[0353] - Figure 13A corresponds to (a) the TOF of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl synthesized in Example 15 and (b) to the TOF of the homogeneous catalyst Re(2,2'-bipyridine)(CO)3Cl) used as a reference;

[0354] - Figure 13B corresponds (a) to the TON of MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl synthesized in example 15 and (b) to the TON of homogeneous catalyst Re(2,2'-bipyridine)(CO)3Cl) used as a reference.

[0355] These results demonstrate that the photocatalytic activity of the hybrid material according to the invention is much higher than that of the reference catalyst. In particular, the rotation frequency (TOF) of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl prepared in Example 15 is 50 times higher than that of the reference catalyst and the rotation number of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl is 2.3 times higher than that of the reference catalyst.

[0356] The results show that the polymer / microporous filler hybrid material (a MOF in this example) according to the invention has improved photocatalytic performance. These results also show that it is possible to achieve photocatalyzed CO2 reduction while easily recovering the catalyst used. Thus, the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl allows for more efficient use of visible light while preserving its structural integrity, in a more sustainable approach.

[0357] Example 17: Use of MOF-containing material as a catalyst in the electrochemical reduction of CO2

[0358] The electrochemical behavior of the hybrid material comprising rhenium synthesized in Example 15 and its electro-catalytic activity was determined during the reduction of CO2.

[0359] The electrocatalytic performance of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) hybrid material in the electrochemical reduction of CO2 was evaluated. To this end, the behavior of the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl hybrid material by cyclic voltammetry under argon or CO2 atmospheres was determined. The results were compared to those obtained for the reference catalyst Re(2,2'-bipyridine)(CO)3Cl. Cyclic voltammetry measurements were performed using a conventional three-electrode electrochemical cell in an anhydrous DMF electrolytic solution containing 0.1 M TBAPF6, with an SP200 potentiostat (Biology). In particular, the cell used comprises a glassy carbon working electrode, a platinum wire counter electrode, and a silver-based quasi-reference electrode (Ag + The cell was filled with a dimethylformamide (DMF) solution containing 0.1 M TBAPF6. Measurements were performed, and the potentials were referenced to ferrocene, which was used as an internal reference and added at the end of each test. The glassy carbon electrode was carefully polished before each use. All measurements were conducted under an inert atmosphere (argon or carbon dioxide) after purging the cell for a minimum of 30 minutes.

[0360] The resulting cyclic voltammograms are shown in Figures 14 to 16, in which:

[0361] - Figure 14 represents the cyclic voltammograms recorded under an argon atmosphere of the reference catalyst (curve (a)) and of the hybrid material including rhenium obtained in example 15 (curve (b)).

[0362] - Figure 15 represents the cyclic voltammograms of the reference catalyst recorded under an argon atmosphere (curve (a)) or under a CO2 atmosphere (curve (b))-

[0363] - Figure 16 represents the cyclic voltammograms of the rhenium-containing hybrid material obtained in Example 15, MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl), recorded under an argon atmosphere (curve (a)) or under a CO2 atmosphere (curve (b)).

[0364] These results show that the cyclic voltammogram of the hybrid material used, recorded under CO2, shows an increase in current from -1.68 V with a positive shift of 580 mV compared to the cyclic voltammogram of the reference catalyst (Figures 15 (b) and 16 (b)).

[0365] The electro-catalytic performance corresponds to the ratio between the catalytic current (icat), measured at the level of the maximum wave, and the reducing peak current (ip) in the absence of substrate.

[0366] These results show an increase in electro-catalytic performance by a factor of 4.48 with a catalytic potential at half height (EI / 2) of -2.1 V for the hybrid material, versus a factor of 3 and an EI / 2 of -2.19 V for the reference catalyst, compared to the black test without catalyst.

[0367] These results indicate that the MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)sCl hybrid material outperforms the reference catalyst Re(2,2'-bipyridine)(CO)sCl for the electrochemical reduction of CO2. The MOF-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl hybrid material exhibits better adsorption, fixation, and / or activation of CO2 than the reference catalyst.

[0368] Furthermore, the rhenium-containing hybrid material obtained in Example 15 exhibits good electrochemical and structural stability, even better electrochemical and structural stability compared to the reference catalyst. The presence of a polymer / filler hybrid material therefore improves the stability of a rhenium-based catalyst.< / greffage>

Claims

Demands 1. A process for preparing a hybrid material comprising a photopolymerization step in which a filler, a photoinitiator, and at least one compound of formula (I) are reacted, the compound of formula (I) being (I) in which, - Ri, R2, R4 and R5, identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms; - R3 and Re, identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, or Rs and Re are linked by a single bond and together represent a -(CH2) group P - (CH2)q- in which p+q = 1 or 2, p being an integer varying from 0 to 2, q being an integer varying from 0 to 2, and p and q not being simultaneously nus, or R3 and Re are linked by a double bond and jointly represent a group -CH2-CH=CH-CH2-; - R? and Rs, whether identical or different, independently represent a hydrogen atom, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula C m X 2m+ i, where X is a halogen and m is an integer ranging from 1 to 6; - R9 and R10, whether identical or different, independently represent a hydrogen, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula C m X 2m+i , where X is a halogen and m is an integer ranging from 1 to 6; - Ri 1 and R12, whether identical or different, independently represent a hydrogen, a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms, a halogen, or a group of formula CmX2m +i in which X is a halogen and m is an integer ranging from 1 to 6; - R13 and Ru, identical, represent a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms or an alkoxy group in which the alkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms; - n represents an integer varying from 0 to 1, the acrylate function being directly linked to the pyridine ring when n is 0 and the acrylate function being linked to R13 or R14 when n is 1.

2. A method for preparing a hybrid material according to claim 1 in which the compound of formula (1) is such that n is equal to 0 and Ri, R2, R3, R4, R5, Re, R7, Rs, R9, R10, Ru and RI2 are as defined in claim 1.

3. A method for preparing a hybrid material according to claim 1 in which the compound of formula (I) is such that n is equal to 1, Ri, R2, R3, R4, R5, Re, R7, Rs, R9, R10, Ru and RI2 are as defined in claim 1 and R13 and R14 represent a linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, preferably CH2.

4. A method for preparing a hybrid material according to any one of claims 1 to 3 wherein the compound of formula (I) is such that Ri, R2, R3, R4, R5 and Re and / or R7, Rs, R9, R10, R11 and RI2 represent hydrogen.

5. A method for preparing a hybrid material according to any one of claims 1 to 4, wherein the compound of formula (I) is such that: - Ri, R2, R3, R4, R5, Re, R7, Rs, R9, R10, Ru, R12 are identical, represent a hydrogen atom, and n is equal to 0, or - Ri, R2, R3, R4, Rs, Re, R7, Re, R9, R10, R11 and RI2 are identical, represent a hydrogen, n is equal to 1 and R13 and R14 represent a CH2.

6. A method for preparing a hybrid material according to any one of claims 1 to 5 wherein the photoinitiator is of the silane type.

7. A process for preparing a hybrid material according to claim 6, wherein the photoinitiator is a compound of formula (A): (A) in which: - Ri represents an alkylene group comprising 1 to 6 carbon atoms or an - O-alkylene group comprising 1 to 6 carbon atoms; - R2 and R3, identical or different, are chosen from the group consisting of: H, NO2, OR a SR a and NR aRb, Ra and Rb, identical or different, representing H or an alkyl group comprising 1 to 6 carbon atoms, or R2 and R3 can together form, with the carbon atoms that bear them, a phenyl group; - n is 0, 1, 2 or 3; - R4 is chosen from the group consisting of: NO2, OR a SR a and NR a Rb, Ra and Rb being as defined above; - R5 and Re, whether identical or different, represent an alkyl group comprising 1 to 6 carbon atoms or an alkoxy group comprising 1 to 6 carbon atoms; and - R7, Rs and R9, identical or different, represent an alkyl or alkoxy group comprising 2 to 6 carbon atoms.

8. A method for preparing a hybrid material according to any one of claims 6 to 7 in which the filler is, prior to the photopolymerization step, bound to the silane-type photoinitiator.

9. A method for preparing a hybrid material according to any one of claims 1 to 8 wherein the filler is a metal-organic structure, a silicate, a silica or a metal oxide, preferably a zeolite.

10. A method for preparing a hybrid material according to any one of claims 1 to 9, wherein the filler is a porous filler whose pores comprise a ligand, preferably a metal cation or a fluorescent molecule.

11. Method for preparing a hybrid material according to any one of claims 1 to 10 comprising prior to the photopolymerization step a complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal.

12. A method for preparing a hybrid material according to any one of claims 1 to 10 comprising, subsequent to the photopolymerization step, a complexation step in which the hybrid material obtained in the photopolymerization step is reacted with at least one transition metal.

13. A method for preparing a hybrid material according to any one of the claims I to 10 including: - prior to the photopolymerization step, a complexation step of the compound of formula (I) in which the compound of formula (I) is reacted with at least one transition metal; - the photopolymerization step in which the compound obtained in the complexation step is reacted with a compound of formula (I) in the presence of the filler and the photoinitiator; and - subsequent to the photopolymerization step, another complexation step in which the hybrid material obtained in the photopolymerization step is reacted with at least one transition metal.

14. A method for preparing a hybrid material according to any one of the claims II to 13, wherein the transition metal is chosen from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium or rhenium.

15. A method for preparing a hybrid material according to any one of claims 1 to 14 wherein the photopolymerization step is carried out, furthermore, in the presence of at least one additional monomer from the acrylic family, this monomer being different from the compound of formula (I).

16. Hybrid material capable of being obtained by a process as defined according to any one of claims 1 to 15.

17. Hybrid material according to claim 16 comprising at least one transition metal.

18. Hybrid material according to claim 17 in which the transition metal is selected from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium or rhenium.

19. Hybrid material according to any one of claims 16 to 18 wherein at least one of the following conditions is met: - the content of the filler is between 10 and 200% by weight relative to the compound of formula (I); - the polymer content is between 10 and 200% by weight relative to the hybrid material; - the mass ratio of filler to polymer is between 4 and 0.

1.

20. Use of a hybrid material according to any one of claims 16 to 19 in at least one of the following applications: - as a ligand; - as a probe or imaging agent; - as a catalyst, preferably for the reduction of CO2, preferably photocatalyzed or electrocatalyzed; - as a photocatalyst, preferably in the photoreduction of CO2 or the photocatalyzed decomposition of water; - as a photosensitizer, particularly in solar cells; - as a component of metal-based medicines; - as an intermediate in the synthesis of supramolecular molecules; - as a basic component of an item obtained by 3D printing; - as a complexing compound for the degradation of pollutants.

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