Researches on Photofunctional and Photocatalytic Chemistry of Metal Complexes as Core Materials

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.