Materials and their use for the electrocatalytic evolution or uptake of H2

A material comprising a solid support of a conductive or semi-conductive material which is functionalized on its surface by linker arms, said linker arms comprising at least two extremities, wherein the first extremity is bonded to the solid support and the second extremity is linked in a covalent manner to a metal-organic complex, wherein the linker arm is selected from molecules responding to the following formulae:

• in which case the interaction between the linker and the solid support is via π-stacking, and to oligomers resulting from the oligomerization of:
• in which case the linker is covalently linked through the Ar group to the solid support,
• wherein:
• Ar represents a C6-C30 aromatic residue, possibly comprising one or more substituants selected from:
• C1-C6 alkyl, —OH, —NH2, —COOH, —F, —Cl, —Br, —I, —NO2, —CONR″2, —COOR″,—SO3−, —SR″, —OR″, —NR″2;
• R and R′, identical or different, represent a group selected from:
• H, C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, C6-C30 aryl, C6-C30 aralkyl, possibly comprising one or more substituants selected from:
• —OH, —NH2, —COOH, —CONH2, triazole, —SH, —N3, and optionally interrupted by one or more bridges selected from:
• —CONH—, —CO—O—, —CO—O—CO—, —CO—NH—CO—, —CO—S—, —CS—O—, and —CS—S—;
• R″ represents a group selected from:
• H, C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, C6-C30 aryl, and C6-C30 aralkyl;
• X represents a group selected from:
• C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, C6-C30 aryl, C6-C30 aralkyl, and optionally comprising one or more substituants selected from:
• —OH,—NH2, —COOH, —CONH2, triazole, —SH, —N3, and optionally interrupted by one or more bridges selected from:
• —CONH—, —CO—O—, —CO—O—CO—, —CO—NH—CO—, —CO—S—, —CS—O—, —CS—S—;
• x is an integer, 1≦x≦5;
• Y is a functional group selected from:
• a simple covalent link, —O—, —NH—, —S—, —COO—,—CONH, —CO—S—, —CS—O—, and —CS—S—,
• and wherein
• the metal-organic complex is selected from those responding to the following formula:
• wherein
• M represents an atom selected from transition metals of the periodic table of elements, and
• R1, R2, identical or different, represent a group selected from:
• H, C1-C20 alkyl, C1-C20 alkenyl, C1-C,20 alkynyl, C6-C30 aryl, C6-C30 aralkyl, optionally comprising one or more functions selected from:
• —OH, —NH2, —COOH , —CONH2, a triazole ring, optionally comprising one or more bridges selected from:
• —CO—O—CO—, —CO—NH—CO—and at least one of the R1 groups or one of the R2 groups represents a covalent link with the linker molecule, two or more R1 substituants can be fused together, two or more R2 substituents can be fused together.