BIPYRIDINES FUNCTIONALIZED BY ACRYLIC FUNCTIONS, THEIR PREPARATION PROCESSES AND THEIR USES

Abstract

ACRYLIC-FUNCTIONALIZED BIPYRIDINES, THEIR PREPARATION PROCESSES AND USES. The invention relates to bipyridine derivatives functionalized with acrylate groups, of formula (I) [Chem 1] (I). The invention also relates to their preparation process and the polymers comprising them, as well as the metal complexes comprising said functionalized bipyridine derivatives, or the polymers comprising them, and their uses. The invention also relates to polymer / filler hybrid materials prepared from these derivatives, as well as the macromolecular metal complexes comprising them and their uses.

Description

Title of the invention: ACRYLIC FUNCTIONALIZED BIPYRIDINES, THEIR PREPARATION METHODS AND THEIR USES TECHNICAL FIELD OF THE INVENTION

[0001] The invention relates to bipyridine derivatives functionalized by acrylate groups, their process of obtaining and the polymers comprising them as well as the metal complexes comprising said functionalized bipyridine derivatives, or the polymers comprising them, as well as their uses.

[0002] The invention also relates to polymer / filler hybrid materials prepared from these functionalized bipyridine derivatives, in which the functionalized bipyridine polymer can form a shell around said filler, as well as to the macromolecular metal complexes comprising them and their uses. STATE OF THE ART

[0003] 2,2'-bipyridine-based ligands comprise two pyridines whose atoms Nitrogens have a strong binding affinity for metals, particularly transition metals. Consequently, they have been extensively studied in the context of metal ion complexation. 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 such as coordination chemistry, supramolecular chemistry, photochemistry, materials chemistry, and catalysis. 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.

[0004] Another potential use of 2,2'-bipyridine-based ligands is catalysis, where bipyridine-based 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.

[0005] These varied applications imply that the properties of the bipyridine can be refined according to the intended use. For example, its polymerization capacity is generally adjusted, notably by the introduction of functional groups onto the pyridine rings.

[0006] The article by AS Maier et al., Macromolecules. 55 (2022) 7039-7048, describes the preparation of a 2.2'-bipyridine-based ligand functionalized with a vinyl function, as well as the Lewis-pair catalyzed polymerization of the ligand and the complexation of the resulting polymer with rhenium and ruthenium.

[0007] The article by M. Antonietti et al. Macromol. Rapid Commun. 16 (1995) 283-289, describes a process for preparing a linear copolymer by microemulsions using 6'-methyl-2,2'-bipyridin-6-ylmethyl methacrylate and a crosslinking agent.

[0008] 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. Existing polymerization processes are therefore poorly suited to certain applications. Therefore, there is a need for a synthesis process for functionalized bipyridines that yields bipyridine derivatives functionalized with desired acrylate groups, and for a polymerization process that can be generalized to the various applications of bipyridine-based materials. Description of the invention

[0009] The present invention aims to remedy all or part of the drawbacks of the prior art cited above. To this end, the invention aims to provide a bipyridine derivative functionalized with acrylate groups whose complexation and / or polymerization properties are improved, while exhibiting good stability properties.

[0010] The invention therefore relates to functionalized bipyridine derivatives of formula (I) [Chem 1] (I)

[0012] in which, - Rb R2, R4 and R5, whether identical or different, independently represent a hydrogen or an alkyl group, - R3 and R6, whether identical or different, independently represent a hydrogen or an alkyl group, or R3 and R6 are linked by a simple bond and together represent a grouping -(CH2)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 nu, or R3 and R6 are linked by a double bond and together represent a grouping -CH2 -CH=CH-CH2-; - R7 and R8, whether identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, 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; - R9 and Rio, whether identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, a halogen, or a group of formula CmX2m+1 in which X is a halogen and m is an integer ranging from 1 to 6; - Ru and R[2, identical or different, independently represent a hydrogen, an alkyl group, an alkoxy group, a halogen or a group of formula CmX2m+1, in which X is a halogen and m is an integer ranging from 1 to 6; - R[3 and Ru, identical, represent an alkyl group or an alkoxy group; - n is an integer ranging from 0 to 1, it being understood that when n = 0 the acrylate group is directly linked to the pyridine ring, and that when n = 1 the acrylate group is linked to Rn or Ru; as well as their preparation process.

[0013] The invention also relates to metal complexes comprising a compound of formula (I) and at least one transition metal, as well as their preparation methods.

[0014] According to another aspect, the invention relates to three-dimensional branched or crosslinked polymers formed from at least one compound of formula (I).

[0015] The invention also relates to a branched or crosslinked polymer comprising or consisting of at least one compound of formula (I) as defined above and / or at least one metal complex of said compound of formula (I).

[0016] According to another aspect, the invention relates to the methods of preparing said compounds of formula (I) as well as the polymers containing them.

[0017] The invention also relates to the metallic complexes of said compounds of formula (I) with at least one transition metal, as well as their preparation methods.

[0018] The invention also relates to hybrid materials comprising a porous or non-porous filler linked to said polymers.

[0019] The invention also relates to macromolecular metal complexes comprising said polymers and at least one transition metal, or comprising a hybrid material and at least one transition metal, as well as their preparation processes and their uses. BRIEF DESCRIPTION OF THE FIGURES

[0020] Fig. 1 represents the kinetics of photopolymerization during the synthesis of the hybrid materials of examples 5 and 6.

[0021] Fig. 2 represents the powder X-ray diffraction (PXRD) spectra of pure zeolite, zeolite grafted with (2,2-dimethyl-l-phenyl-5-(triethyloxysilyl)pentan-l-one and hybrid materials prepared in Examples 5 and 6.

[0022] Fig. 3 represents the Fourier transform infrared (FTIR) spectroscopy spectra of pure zeolite, zeolite grafted with (2,2-dimethyl-l-phenyl-5-(triethyloxysilyl)pentan-l-one and hybrid materials prepared in Examples 5 and 6.

[0023] Fig. 4 represents the adsorption / desorption isotherm of N2 on pure zeolite and on the macromolecular metal complexes prepared in Examples 9 and 12.

[0024] Fig. 5 represents the CO2 absorption isotherm on pure zeolite and on the macromolecular metal complexes prepared in Examples 9 and 12.

[0025] Fig. 6 represents the evolution of the quantity of CO produced during the photocatalytic reduction of CO2 under visible light (LED 405 nm) on the macromolecular metal complexes prepared in examples 9, 10 and 12.

[0026] Fig. 7 represents the evolution of the quantity of CO produced during the photocatalytic reduction of CO2 catalyzed by the macromolecular metal complex prepared in example 9. DETAILED DESCRIPTION OF THE INVENTION

[0027] It has now been found that the functionalization of a 2,2'-bipyridine compound by acrylate groups in position 4, 4' makes it possible to obtain a functionalized compound which, due to its structure, is able to be (photo)polymerized, 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.

[0028] Advantageously, the polymer obtained from the 2,2'-bipyridine compound functionalized with acrylic functions according to the invention is three-dimensional.

[0029] It has also been found that the 2,2'-bipyridine compound functionalized with acrylic groups according to the invention can complex with transition metals in significant 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.

[0030] It has also been found that the macromolecular metal complexes and hybrid materials obtained from the 2,2'-bipyridine compound functionalized with acrylic functions according to the invention advantageously exhibit catalytic activity, particularly in the context of the photocatalytic reduction of CO2.

[0031] Furthermore, a process for synthesizing 2,2'-bipyridine derivatives functionalized with acrylic groups has been found which is simple, non-toxic, suitable for industrial implementation, and which allows obtaining a product of high purity.

[0032] Advantageously, the functionalized 2,2'-bipyridine derivatives may comprise two identical or different acrylic functions.

[0033] In the rest of the description, the terms “acrylic function”, “acrylate function”, “acrylic group” or “acrylate group” will be used interchangeably.

[0034] The term "comprising" is understood, for the purposes of this description, as encompassing the terms "containing", "made up of" or "consisting of".

[0035] The terms "made of" or "consisting of", in the context of this description, exclude the presence of any other characteristics than those that follow this formulation.

[0036] Unless otherwise stipulated, the indicated value ranges are understood to include the limits.

[0037] The invention therefore relates, according to one aspect, to a compound of formula (I)

[0038] [Chem 1] (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 R6, identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, or R3 and R6 are linked by a single bond and jointly represent a -(CH2)P - (CH2)q- group 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 harmed, or R3 and R6 are linked by a double bond and jointly represent a -CH2 -CH=CH-CH2- group; - R7 and R8, 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; - R9 and Rio, 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; - Rn and Rn, 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+1 in which X is a halogen and m is an integer ranging from 1 to 6; - Rn and Rm, 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 ranging 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 Rn or RM when n is 1.

[0039] By "linear or branched alkyl, saturated or unsaturated, comprising 1 to 6 carbon atoms", means, 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.

[0040] By "halogen" is meant an atom of fluorine, chlorine, bromine or iodine.

[0041] Preferably, in formula (I) above, n is equal to 0 and RB R2, R3, R4, R5, R6, R7 , R8, R9, Rio, Rn and Rn are as defined above.

[0042] The compounds of formula (I) correspond in this case to the formula (LA) below: [Chem 2] R? (THERE)

[0043] According to another preferred aspect, in formula (I) above, n is equal to 1, Rb R2, R3, R4, R5, R6, R?, R8, R9, Rio, Ru and R[2 are as defined above and Rn and R[4 represent a linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, preferably CH2. Advantageous compounds of formula (I) are those in which n equals 1. Rb, R2, R3, R4, R5, R6, R7, R8, R9, Rio, Ru, and R12 are as defined above, and R13 and R14 represent CH2. These compounds correspond to formula (IB) below: [Chem 3]

[0044]

[0045]

[0046] (IB) Compounds of formula (I) in which Rb R2, R3, Ri, R5 and R6 and / or R7, R8, R9, Rio, Ru and R[2 represent hydrogen are advantageous compounds of the invention. Other compounds of formula (I) in which - Rb, R2, R3, Ri, R5, R6, R7, R8, R9, Rio, Ru, Ri2 (identical), represent a hydrogen and n = 0, or - Rb R2, R3, R, R5, R6, R7, R8, R9, Rio, Ru and R[2 identical, represent a hydrogen, n = 1 and R[3 and R[4 represent CH2, are also advantageous compounds according to the invention. The invention also relates to a method for preparing a compound of formula (I) as defined above [Chem 1]

[0047] Ry O (I) in which - Rb R2, R3, R4, R5, Re, R13, Ru and n, are as defined above; - R7 and R8 are as defined above and are identical. - R9 and Rio are as defined above and are identical, and - Rn and Rn are as defined above and are identical, comprising: - the reaction of a compound of formula (II) [Chem 4] H y (II)

[0048] with an acrylic acid derivative of formula (III) [Chem 5] K (in) in which - Rb R2, R3, R4, R5, Re, R7, R9, Ru, R13, Ru and n, are as defined above; - 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).

[0049] According to one aspect of the process of the invention, R7, R8, R9, R10, Ru and Rn are identical, and represent, in particular, hydrogen.

[0050] For example, a base such as diisopropylethylamine (DIPEA) or triethylamine (TEA) will be used.

[0051] 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.

[0052] The excess of acrylic acid derivative relative to the compound of formula (II) may, for example, be between 5 to 8 equivalents of acrylic acid derivative for 1 equivalent of compound of formula (II), in particular 5 to 7 equivalents of acrylic acid derivative for 1 equivalent of compound of formula (II), in particular 7 equivalents of acrylic acid derivative for 1 equivalent of compound of formula (II).

[0053] The excess of base with respect to the compound of formula (II) may, for example, be between 5 to 8 equivalents of base for 1 equivalent of compound of formula 2, in particular 5 to 7 equivalents of base for 1 equivalent of compound of formula (II), in particular 5 equivalents of base for 1 equivalent of compound of formula (II).

[0054] The invention also relates to a method for preparing a compound of formula (I) as described above [Chem 1]

[0055] O (i) in which Rb, R2, R3, R4, R5, R6, R7, R8, R9, Rio, R11, R12, Rb, Ru, and n are as defined above, and at least one of the substituents R7, R9, and Rn is different from at least one of the substituents R8, Rio, and R12, comprising - a step of preparing the compound of formula (VI) [Chem 6] R- 0

[0056] (VI) in which - Rb R2, R3, R4, R5, R6, R7, R9, Ru, Rn, Ru and n are as defined above; - R15 represents a protecting group, in particular a linear alkyl group or branched, saturated or unsaturated, comprising 1 to 6 carbon atoms, either unsubstituted or substituted with 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) [Chem 7] (V) in which RB R2, R3, R4, R5, R6, R13, Ru, R15 and n are such as defined above for formula (I);

[0057] with an acrylic acid derivative of formula (III) [Chem 5] R? O V / / \ / / P \ r3— / / x \ Ru (III) in which - R7, R9, and Ru 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 (VI) by elimination of the protecting group Ri5 [Chem 8] (VII) in which R2, R3, R4, R5, R6, R7, R% Ru, Rb, Ru and n are such as defined above; and - the reaction of the compound of formula (VII) with an acrylic acid derivative of formula (IV) [Chem 9] 9 Rs

[0058] ^2 (IV) in which - R8, Rio and Rn are as defined above; - 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 (VII). In particular, by "aryl group" we mean for example a benzyl, a phenyl, a tolyl, a xylyl or a naphthyl.

[0059] 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 Ri5.

[0060] In particular, the protecting group Ri5 is chosen such that O-Ri5 forms an acetal, an aryl ether or a silyl ether.

[0061] In particular, when O-Ri5 forms a silyl ether, R[5] 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.

[0062] In particular, when O-Ri5 forms an aryl ether, preferably a benzyl ether, Ri5 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 Talkyl is linear or branched, saturated or unsaturated, and comprises 1 to 6 carbon atoms. Preferably, R[5] 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).

[0063] In particular, when O-R15 forms an acetal, Ri5 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, R[5] can be a chloromethyl ether (M0M-C1) or an oxane such as tetrahydropyran (THP).

[0064] In particular, when Ri5 is tetrahydropyran (THP), the compound of formula (V) can be prepared from the reaction of dihydropyran with the compound of formula (II) in the presence of an acid, such as para-toluenesulfonic acid, in an organic solvent, such as chloroform. The compound (VII) can be prepared by deprotection from the compound of formula (VI) in the presence of an acid, such as para-toluenesulfonic acid, in an organic solvent, such as methanol. The deprotection conditions (removal of the protecting group Ri5) mentioned above are common in the field.

[0065] The general and specific aspects relating to the base, the solvent, and the acrylic derivative, as defined above for the process of preparing a compound of formula (I) as described above, in which R7 and R8 are identical, R9 and R10 are identical, and R and R12 are identical, also apply to the process of preparation of a compound of formula (I) in which R7, R8, R9, R10, Ru and Rn are not all identical.

[0066] Preferably, in the process according to the invention, at least one of the following conditions is met: - the base is triethylamine (TEA); - 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; - 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; - the derivative of acrylic acid is acryloyl chloride.

[0067] The invention also relates to a metallic complex comprising a compound of formula (I) as described above and at least one transition metal.

[0068] Said transition metal may be, for example, chosen from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium or rhenium.

[0069] Said metal complex can be prepared by a conventional method, by bringing said compound of formula (I) into contact with said 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. The invention also relates, according to another aspect, to a branched or crosslinked polymer formed from at least one compound of formula (I) as described above or obtained by the process described above.

[0070] The invention also relates to 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). The general and specific aspects of the invention described above apply equally to the compounds of formula (I), their preparation process, and the polymers comprising them.

[0071] The invention also relates to a hybrid material comprising a porous or non-porous filler bonded to a polymer as described above. In particular, the invention relates to such a hybrid material in which the filler is an inorganic particle, for example, a metal-organic structure, a silicate, a silica, or a metal oxide, preferably a zeolite. In particular, the metal-organic structure, also called a metal-organic framework (MOF) In English, it is preferably titanium- or zirconium-based. When the filler is a metal-organic structure, the filler is, for example, of the Universitetet i Oslo (UiO-66), MIL-125, MIL-100, MIL-101, MIL-177 type and their derivatives. Advantageously, said charge is a porous charge whose pores may comprise an organic molecule, in particular a metal ion or a fluorescent molecule.

[0072] A preferred hybrid material according to the invention is one in which 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.

[0073] The invention also relates to a macromolecular metal complex comprising at least one polymer as defined above and at least one transition metal or at least one hybrid material as defined above and at least one transition metal.

[0074] Advantageously, said 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.

[0075] An advantageous macromolecular metal complex according to the invention is one in which at least one of the following conditions is met: - the complex comprises at least two metals; - the polymer is as defined above; - the charge is a zeolite; - the transition metal(s) are Ru(II) and / or Re(II).

[0076] The general and particular aspects of the invention described above apply equally to compounds of formula (I), to metal complexes comprising them, to macromolecular metal complexes comprising polymers based on compounds of formula (I), to hybrid materials comprising a porous or non-porous filler linked to said polymer and also to macromolecular metal complexes comprising said hybrid materials.

[0077] The polymer comprising or consisting of at least one compound of formula (I) and / or at least one metal complex of 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 complex is reacted metallic, with at least one photoinitiator under light irradiation. The photoinitiator may be immobilized or unimmobilized on a charge.

[0078] The invention also relates to a method for preparing a hybrid material as described above comprising a photopolymerization step in which: 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 photoinitiator or initiator free or immobilized on a charge and light irradiation. The term “photoinitiator” means an organic or mineral compound which, in combination with light irradiation, initiates the polymerization of the compound of formula (I) and / or the complex described above.

[0079] The term "initiator" means an organic or mineral compound which, under thermal effect, has the effect of initiating the polymerization of the compound of formula (I) and / or of the complex described above. The (photo)initiator can be any (photo)initiator commonly used in radical (photo)polymerization. Preferably, the (photo)initiator is immobilized on a charge. In this case, the (photo)initiator is preferably of the silane type.

[0080] Preferably, in said process, at least one of the following conditions is met: - the charge is previously linked to the silane-type photoinitiator; - 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; - the photoinitiator content is 6% to 10% by weight relative to the weight of the charge; - the photopolymerization step is carried out in solution in the presence of an organic solvent, preferably acetonitrile; - the light irradiation is monochromatic or polychromatic; - the photopolymerization step is carried out, in addition, in the presence of at least one additional comonomer from the acrylic family; - the photopolymerization step is carried out, in addition, in the presence of at least one metallic complex as described above.

[0081] The invention also relates to a method for preparing a metal complex comprising a compound of formula (I) as described above and at least one transition metal, or a method for preparing a macromolecular metal complex comprising at least one polymer as defined above and at least one transition metal, or at least one hybrid material as defined above and at least one transition metal, comprising: - the reaction of a compound of formula (I) as described above with a transition metal; or - the reaction of a polymer as described above with a transition metal; or - 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 or rhenium.

[0082] According to one aspect of it, the invention also relates to the use of a compound of formula (I) as described above, or of a metal complex comprising a compound of formula (I) as described above, or of a polymer comprising or consisting of at least one compound of formula (I) as described above, or of a hybrid material as described above, or of a macromolecular metal complex as described above, in at least one of the following applications: - as a ligand; - as a probe or imaging agent; - 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.

[0083] The invention is illustrated in a non-limiting way by the following examples. EXAMPLES

[0084] Example 1: Synthesis of the compound [2,2'-bipyridine]-4,4'-diyldiacrylate

[0085] The compound [2,2'-bipyridine]-4,4'-diyldiacrylate was synthesized in one step from [2,2'-Bipyridine]-4,4'-diol (commercially available). 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 MgSO4. 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 as eluting a dichloromethane:methanol (98:2) mixture. The final pure product is obtained with a yield of 42% in the form of a white solid with a purity of 99%.

[0086] 'H NMR (500 MHz, DMSO-d6) ô: 8.79 (d, 2H, J = 5.4 Hz), 8.28 (d, 2H, J = 1.95 Hz), 7.46 (dd, 2H, J! = 5.2 Hz, J2 = 2.15 Hz), 6.66 (d, 2H, J = 17.21 Hz), 6.5 (dd, 2H, J! = 17.21 Hz, J2 =10.4 Hz), 6.28 (d, 2H, J = 10.45 Hz).

[0087] Example 2: Synthesis of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate

[0088] The compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate was synthesized in one step from 2,2'-Bipyridine-4,4'-dimethanol.

[0089] A solution of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (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 MgSO4. 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%.

[0090] [Chem. 10]

[0091] *H NMR (500 MHz, DMSO-d6) ô: 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 = 17.41 Hz), 6.36 (dd, 2H, J! = 17.15 Hz, J2 =10.3 Hz), 6.08 (d, 2H, J = 10.4 Hz), 5.39 (s, 4H). 13C NMR (125 MHz, DMSO-d6) δ: 166.15 (C=O); 156.05; 150.50; 147.41; 133.50; 128.78; 123.36; 119.48; 65.09 (CH2). HRMS (ESI+): calculated from [M+H]+= 325.11 ; found =325.1186.

[0092] Example 3: Synthesis of the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)Re(CO)3Cl

[0093] 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(I) (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)3Cl, whose formula is given below, is obtained with a yield of 82% and a purity greater than 99%.

[0094] [Chem. 11]

[0095] The results show that the compound according to the invention 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.

[0096] *H NMR (500 MHz, DMSO-d6) ô: 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, J! = 17.42 Hz, J2=10.59 Hz), 6.03 (d, 2H, J = 10.48 Hz), 5.44 (s, 4H). 13C NMR (125 MHz, DMSO-d6) δ: 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).

[0097]

[0098] HRMS (ESI+): calculated from [M+H]+ = 653.02; found = 653.0098 Example 4: Synthesis of the complex ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine) 2 RuCl 2 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%. [Chem 12]

[0099] The results show that the compound of the invention 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.

[0100] *H NMR (500 MHz, DMSO-d6) ô: 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 (d, 2H, J = 6.03 Hz), 7.74 (d, 2H, J = 5.22 Hz), 7.56 (m, 6H), 6.49 (d, 2H, J = 17.34 Hz), 6.34 (dd, 2H, J! = 17.11 Hz, J2 =10.29 Hz), 6.10 (d, 2H, J = 10.33 Hz), 5.46 (s, 4H). 13C NMR (125 MHz, DMSO-d6) ô: 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 (CH2). HRMS (ES+): calculated from [M / 2] = 369.0745, found = 369.0769.

[0101] Example 5: Synthesis and characterization of the hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)

[0102] The hybrid material consisting of a zeolite (Faujasite X), hereinafter referred to as "ZX", linked to a poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) was obtained by the photopolymerization of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate obtained in Example 2. The polymerization yield of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate, determined according to the procedure described in Example 8 below, is 60%.

[0103] Preparation of the zeolite 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 SiO2: 1.1 Al2O3: 9 Na2O: 122 H2O. Zeolite grafting The zeolite thus prepared was then linked to silane-type photoinitiators. The dried zeolite (1g, 1 equivalent) is dehydrated at 150°C under constant stirring. A silane-type photoinitiator, SPL1 (2,2-dimethyl-l-phenyl-5-(triethyloxysi lyl)pentan-lone, 0.275 mmol, 1 equivalent), described in application WO2019 / 097021.

[0104] is dissolved in ethanol (1 mL). This solution is dispersed onto 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. 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.

[0105] Photopolymerization of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate The hybrid material ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) was then prepared by photopolymerization. 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 / cm³ while maintaining stirring 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 is then dried at 50°C for 12 hours.

[0106] Polymerization kinetics A monitoring of the photopolymerization kinetics of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer 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. The polymerization process of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate is shown in [Fig. 1], in which: - 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 of example 5; - 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 of example 6 below. This result ([Fig.l] 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.

[0107] Characterization of the crystallinity and purity of the hybrid material The crystallinity and purity of the ZX-poly([2,2'-bipyridine]-4,4'-diyl bis(methylene) diacrylate) hybrid material obtained were characterized by powder X-ray diffraction (PXRD) analysis and by Fourier transform infrared (FTIR) spectroscopy. PXRD analysis was performed using a PANalytical X'Pert Pro diffractometer with a mean XCuKa 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-variol diffractometer equipped with a a primary germanium (111) Johansson monochromator with a wavelength XKal = 1.5406 Å and a LynxEye detector. PXRD patterns were recorded at room temperature between 3 and 120° (20) with a step size of approximately 0.014° (20). Variable diverging slits with a constant illuminated sample length of 6 mm were used. Phase identifications were performed with the PANalytical HighScore plus program. The powder X-ray diffraction (PXRD) spectrum of the obtained ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material is shown in [Fig. 2], in which: - curve (a) is the diffraction spectrum of the pure zeolite; - curve (b) is the diffraction spectrum of the zeolite grafted with the SPL1 photoinitiator; - Curve (c) is the diffraction spectrum of the zeolite grafted with the SPL1 photoinitiator 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 SPL1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and di(trimethylolpropane) tetraacrylate (from example 6 below). For FTIR analysis, the powdered product was compressed to approximately 107 Pa / cm², placed in a self-supporting disk (2 cm² area, approximately 20 mg), and loaded into 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 cm¹ at a resolution of 4 cm⁻¹. The FTIR spectra are shown in [Fig.3], in which: - curve (a) represents the FTIR spectrum of pure zeolite; - curve (b) represents the FTIR spectrum of the zeolite grafted with the SPL1 photoinitiator; - Curve (c) represents the FTIR spectrum of the zeolite grafted with the SPL1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate; and - curve (d) represents the FTIR spectrum of the zeolite grafted with the SPL1 photoinitiator after photopolymerization with the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and the di(trimethylolpropane) tetraacrylate (from example 6 below). The results obtained confirm the production of a pure solid and the preservation of the zeolite's crystalline structure. The results also show that the Photopolymerization on the zeolite of the bipyridine derivative from Example 2 does not affect the structure of the filler.

[0108] Example 6: Synthesis of the hybrid copolymer material of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and DMPTA on a zeolite

[0109] 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%.

[0110] The preparation and grafting of a nanoparticulate zeolite X of the Faujasite type were carried out as in Example 5. During the photopolymerization step, the procedure described in Example 5 was carried out by adding this time the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate (20 mg) and DTMPTA (100 mg) to the zeolite solution.

[0111] The yield of the photopolymerization of the compound [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and the content of bipyridines in the hybrid material were calculated as in Example 5. Polymerization kinetics Monitoring of the photopolymerization kinetics of the [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate monomer 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. The evolution of the polymerization of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate shown in [Fig.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.

[0112] Crystallinity and purity of the hybrid material The crystallinity and purity of the resulting ZX-poly([2,2'-bipyridine]-4,4'-diyl bis(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.

[0113] Example 7: Synthesis of a hybrid material of a copolymer of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and of ([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 on a zeolite.

[0114] 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 [2,2'-bipyridine] derivatives in complexed and uncomplexed form, determined according to the procedure described in Example 8 below, is 40%.

[0115] 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 carried out by adding this time 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.

[0116] 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) 2 RuCl 2

[0117] 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 the ji-ji* transitions centered in the heterocyclic ligands before (Io) and after (I) photopolymerization, using the equation: photopolymerization yield (%) = x 100. 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 residual unpolymerized amount. The yields thus calculated from the photopolymerization of [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate and / or [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)(bipyridine)2RuCl2 during the preparation of the ZX-poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) hybrid material of Example 5, of the material hybrid of example 6 and hybrid material of example 7 are reported in table (1).

[0118] [Tables 1] Hybrid material Example 6 Example 7 Example 8 Photopolymerization yield (%) 65 85 40 Bipyridine content (mmol / g) 0.6 0.75 0.3

[0119] These results show that the bipyridine derivatives synthesized in examples 2 and 4 are capable of polymerizing. 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.

[0120] Example 9: Synthesis of the macromolecular metal complex ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) by complexation of the hybrid material of Example 5 with rhenium

[0121] 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(I) (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. The pure final product, ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl), 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.

[0122] Accessibility of zeolite pores 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)3Cl macromolecular metal complex). These analyses allow us to evaluate 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)3Cl macromolecular metal complex) prepared in Example 12 below were used as controls. The adsorption / desorption isotherm of N2 on the zeolite is shown in [Fig. 4], in which: - curve (a) represents the absorption / desorption isotherm of N2 on pure zeolite (from example 5); - Curve (b) represents the absorption / desorption isotherm of N2 on the macromolecular metal complex ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl); and - curve (c) represents the absorption / desorption isotherm of N2 on the macromolecular metal complex poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) (from example 12 below). The CO2 adsorption isotherm on the zeolite is shown in [Fig. 5], in which: - curve (a) represents the absorption / desorption isotherm of CO2 on pure zeolite (from example 5); - Curve (b) represents the CO2 absorption / desorption isotherm on the macromolecular metal complex ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl); and - curve (c) represents the absorption / desorption isotherm of CO2 on the macromolecular metal complex poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) (from example 12 below). 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)3Cl). Therefore, the presence of the polymer on the porous filler does not affect the accessibility of the filler's porosity.

[0123] Example 10: Complexation of the hybrid material of Example 7 with rhenium

[0124] A solution of the material of Example 7 (100 mg, 1 equivalent) in toluene (6 mL) and excess pentacarbonylchlororhenium(I) (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. 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. The complex thus formed comprises two transition metals: rhenium and ruthenium.

[0125] Example 11: Synthesis of filler-free polymer: poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate)

[0126] Preparation of poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) 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 / cm³ while maintaining stirring 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 is then dried at 50°C for 12 hours before being characterized.

[0127] Photopolymerization yield of the monomer [2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate 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%. 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.

[0128] Example 12: Synthesis of the macromolecular metal complex poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO) 3 Cl)

[0129] A solution of poly([2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate) (0.048 mmol) obtained in Example 11 in toluene and pentacarbonylchlororhenium(I) (Re(CO)5Cl, in excess) (0.058 mmol) 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. The yield of the complexation reaction, determined according to the procedure described in Example 13 below, is 50%.

[0130] Example 13: Yield of the complexation reaction and rhenium content

[0131] 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 vibration of the C=O bond at 2025cm*. Each product obtained in powder form was pressed to approximately 107 Pa / cm², then introduced into a self-supporting disk (area of ​​2 cm², approximately 20 mg) and subsequently placed in an IR cell of a Nicolet 6700 IR spectrometer equipped with a detector DTGS (for "Deuterated Triglycine Sulfate") 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 from 400 to 5500 cm¹ at a resolution of 4 cm⁻¹. 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.

[0132] [Tables2] Macromolecular metal complex Example 9 Example 10 Example 12 Yield (%) 50 67 50 Content (mmol / g) 0.3 0.2 /

[0133] 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. 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 zeolite (Examples 9 and 12). Therefore, the presence of the filler does not affect the efficiency of the complexation of bipyridine derivatives. Furthermore, the results show that it is possible to obtain a macromolecular metal complex comprising two different transition metals from the bipyridine derivative prepared in Example 2 (Example 10).

[0134] Example 14: Use of macromolecular metal complexes as catalysts in the photocatalyzed reduction of CO2

[0135] The photocatalytic performance of the macromolecular metal complexes synthesized in Examples 9, 10 and 12 was determined during the photocatalytic reduction of CO2. 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 controlled 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 complex synthesized in Example 9 (3 mg), Example 10 (3 mg), or 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 a donor electrons (220 mg in 1 mL) were released while maintaining CO2 bubbling for 15 min. The photocatalyzed reduction of CO2 was performed three times for each macromolecular metal complex used. The error values ​​obtained were less than 10%, demonstrating high reproducibility of the reaction.

[0136] 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 [Fig. 6], in which: - curve (a) represents the reduction of CO2 photocatalyzed by the macromolecular metal complex poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) (from example 12); - curve (b) represents the reduction of CO2 photocatalyzed by the macromolecular metal complex ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) (from example 9); and - curve (c) represents the reduction of CO2 photocatalyzed by the macromolecular metal complex comprising rhenium and ruthenium (from example 10). The stability of the photocatalytic activity of the macromolecular metal complex ZX-poly([[2,2'-bipyridine]-4,4'-diylbis(methylene) diacrylate]Re(CO)3Cl) (from example 9) as a catalyst is shown in [Fig.7].

[0137] 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 macromolecular metal complexes according to the invention is stable over time.

Claims

1. Demands Compound of formula (I) [Chem.l] (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 R6, whether identical or different, independently represent a hydrogen or a linear or branched alkyl group, saturated or unsaturated, comprising 1 to 6 carbon atoms, or R3 and R6 are linked by a single bond and jointly represent a -(CH2)P - (CH2)q- group in which p+q = 1 or 2, p being an integer ranging from 0 to 2, q being an integer ranging from 0 to 2, and p and q not being simultaneously nu, or R3 and R6 are linked by a double bond and together represent a -CH2 -CH=CH-CH2- group; - R7 and R8, 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+1, in which X is a halogen and m is an integer ranging from 1 to 6; - R9 and Rio, 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 from 1 to 6; - Ri i and Rn, 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 from 1 to 6; - Rn 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 ranging from 0 to 1, the acrylate function being directly linked to the pyridine ring when n equals 0 and the acrylate function being linked to Rn or RM when n equals 1.;

2. Compound of formula (I) according to claim 1, in which n is equal to 0 and Ri, R2, R3, R4, R5, R6, R7, R8, R9, R10, Rn and R12 are as defined in claim 1.

3. Compound of formula (I) according to claim 1, in which n is equal to 1, Ri, R2, R3, R4, R5, R6, R7, R8, R9, Rio, Rn and R14 are as defined in claim 1 and Rn and R14 represent a linear or branched, saturated or unsaturated alkyl group comprising 1 to 6 carbon atoms, preferably CH2.

4. Compound of formula (I) according to any one of claims 1 to 3 wherein RH R2, R3, R4, R5 and R6 and / or R7, R8, R9, R10, Rn and R[2 represent hydrogen.

5. Compound of formula (I) according to any one of claims 1 to 4 wherein: - Ri, R2, R3, R4, R5, R6, R7, R8, R9, Rio, Rn, R12 identical, represent a hydrogen and n is equal to 0, or - Rb R2, R3, R4, R5, R6, R7, R8, R9, Rio, Rn and R[2 identical, represent a hydrogen, n is equal to 1 and R[3 and R[4 represent a ch2.

6.

7.

8. Metallic complex comprising a compound of formula (I) according to any one of claims 1 to 5 and at least one transition metal. Metallic complex according to claim 6, wherein 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. Method for preparing a compound of formula (I) according to any one of claims 1 to 5, [Chem 1] R- O / s (I) in which - Ri, R2, R3, R4, R5, R6, Rb, Ru and n, are as defined in any one of claims 1 to 5; - R7 and R8 are as defined in any one of claims 1 to 5 and are identical, - R9 and Rio are as defined in any one of claims 1 to 5 and are identical, and - Ru and Rn are as defined in any one of claims 1 to 5 and are identical, comprising: - the reaction of a compound of formula (II) [Chem 4] (II) with an acrylic acid derivative of formula (III) [Chem 5] R? 0 Z.

9. (III) in which - Ri, R2, R3, R4, R5, R6, R7, R9, Ru, Rb, Ru and n, are as defined above; - 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). Method for preparing a compound of formula (I) according to any one of claims 1 to 4 [Chem 1] R? O (I) in which Rb, R2, R3, R4, R5, Re, R7, Rs, R9, Rio, R11, R12, Rio, R14 and n are as defined according to any one of claims 1 to 4, and at least one of the substituents R7, R9 and Rn is different from at least one of the substituents R8, RiO and Rn, comprising - a step of preparing the compound of formula (VI) [Chem 6] (VI) in which Ri, R2, R3, R4, R5, Re, R7, R% Ru, Rb, Ru and n are as defined above; Rb 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) [Chem 7] (V) in which Rb, R2, R3, R4, R5, R6, R13, Ru, RbêI n are as defined in any one of claims 1 to 5 with an acrylic acid derivative of formula (III) [Chem 5] (III) in which R7, R9, and Ru are as defined above; 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 (VI) by removing the protecting group R15 [Chem 8] R- O (VII) in which Rb, R2, R3, R4, R5, R6, R7, R9, Ru, Rb, Ru and n are as defined above; and - the reaction of the compound of formula (VII) with an acrylic acid derivative of formula (IV) [Chem 9] (IV) in which R8, Rio and R[2, are as defined above; 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 (VII).

10. A process according to any one of claims 8 or 9 wherein at least one of the following conditions is met: - the base is triethylamine; - 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; - 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; - the organic solvent is chloroform; - the acrylic acid derivative is acryloyl chloride.

11. Branched or crosslinked polymer formed from at least one compound of formula (I) according to any one of claims 1 to 5 or obtained according to any one of claims 8 to 10.

12. Branched or crosslinked polymer according to claim 11 comprising or consisting of at least one compound of formula (I) according to any one of claims 1 to 5 and / or at least one metal complex of the compound of formula (I) according to any one of claims 6 or 7.

13. Hybrid material comprising a porous or non-porous filler bonded to a polymer according to any one of claims 11 or 12.

14. Hybrid material according to claim 13 in which the filler is a metal-organic structure, a silicate, a silica or a metal oxide, preferably a zeolite.

15. Hybrid material according to any one of claims 13 or 14 wherein the filler is a porous filler whose pores comprise a ligand, preferably a metal cation or a fluorescent molecule.

16. Hybrid material according to any one of claims 13 to 15 wherein at least one of the following conditions is met: - the filler content 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 filler / polymer mass ratio is between 4 and 0.

1.

17. Macromolecular metal complex comprising at least one polymer according to any one of claims 12 or 13 and at least one transition metal or at least one hybrid material according to any one of claims 14 to 17 and at least one transition metal.

18. A method for preparing a hybrid material according to any one of claims 13 to 16 comprising a polymerization or photopolymerization step in which: at least one filler is reacted with at least one compound of formula (I) according to any one of claims 1 to 5 and / or at least one complex according to any one of claims 6 or 7, in the presence of at least one initiator, or at least one photoinitiator and light irradiation.

19. A method for preparing a hybrid material according to claim 18, wherein at least one of the following conditions is met: - the filler is pre-bonded to the silane-type photoinitiator; - the photoinitiator content is 0.1 to 2% by weight relative to the weight of the compound of formula (I) and / or the complex of the compound of formula (I) as described above; - the photoinitiator content is 6% to 10% by weight relative to the weight of the filler; - the photopolymerization step is carried out in solution in the presence of an organic solvent, preferably acetonitrile; - the light irradiation is monochromatic or polychromatic irradiation; - the photopolymerization step is carried out, in addition, in the presence of at least one additional comonomer from the family of acrylic acids; - the photopolymerization step is carried out, in addition, in the presence of at least one complex according to claims 6 or 7.

20. A method for preparing a metal complex according to claim 6 or 7 or a macromolecular metal complex according to claim 17, comprising: - the reaction of a compound of formula (I) according to any one of claims 1 to 5 with a transition metal; or - the reaction of a polymer according to any one of claims 11 or 12 with a transition metal; or - the reaction of a hybrid material according to any one of claims 13 to 16 with a transition metal, said transition metal being selected from titanium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, iridium, rhodium, palladium, silver, rhenium, osmium, platinum and gold, preferably ruthenium or rhenium.

21. Use of a compound of formula (I) according to any one of claims 1 to 5, or of a metal complex according to claim 6 or 7, or of a polymer according to any one of claims 11 or 12, or of a hybrid material according to any one of claims 13 to 16, or of a macromolecular metal complex according to claim 17 in at least one of the following applications: - as a ligand; - as a probe or imaging agent; - 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 drugs; - as a synthetic intermediate for 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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