Abstract

We found the following new photochemical reactions and photophysical properties of transition metal complexes: (1) photochemical formation of Ru(II) hydride complexes, (2) photochemical ligand substitution reactions of the Re(I)diiminetricarbonyl complexes, and (3) control of photophysical and electrochemical properties of metal complexes by introducing p-p interaction between ligands. Application of these reactions and photophysical properties of transition metal complexes enabled us to synthesize new photofunctional metal-complex oligomers and polymers, and to develop efficient, durable, and highly selective photocatalysts for hydride reduction of NAD(P)+ models and CO2 reduction. We also succeeded construction of new photofunctional hybrids of the metal-complex photocatalysts with various solid materials, i.e. semiconductor-particle photocatalysts, p-type semiconductor electrodes, and mesoporous organosilica, which can drive photocatalytic reduction of CO2 via Z-scheme electron transfer, photocatalytic CO2 reduction by using water as a reductant and visible light as energy, and lightenergy accumulation for photocatalytic CO2 reduction, respectively.

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