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The photocatalytic reduction of carbon dioxide (CO 2 ) to value-added chemicals is an attractive strategy to utilize CO 2  as a feedstock for storing renewable energy, such as solar energy, in chemical bonds. Inspired by the biological function of the nicotinamide adenine dinucleotide redox couple (NAD + /NADH), we have been developing transition-metal complexes containing NAD + /NADH-functionalized ligands to create electro- and/or photochemically renewable hydride donors for the conversion of CO 2  into value-added chemicals. Our previous findings have provided insights for the development of photocatalytic organic hydride reduction reactions for CO 2 , however, further examples, as well as investigation, of these photo-driven NAD + /NADH-type hydrogenation and organic hydride transfer reactions are required not only to explore the mechanism in detail but also to develop a highly efficient catalyst for artificial photosynthesis. In this paper, we report the synthesis, characterization, and photo-induced NAD + /NADH conversion properties of a new ruthenium(II) complex, [Ru(bpy) 2 (Me-pn)](PF 6 ) 2  ( 1 ), which contains a new NAD + -type ligand, Me-pn (2-methyl-6-(pyridin-2-yl)-1,5-naphthyridine). In addition, we have succeeded in the isolation of the corresponding two-electron reduced ruthenium(II) complex containing the NADH-type ligand Me-pnHH (2-methyl-6-(pyridin-2-yl)-1,4-dihydro-1,5-naphthyridine), i.e., [Ru(bpy) 2 (Me-pnHH)](PF 6 ) 2  ( 1HH ), by the photo-induced hydrogenation reaction of  1 . Thus, in this study, a new photo-driven NAD + /NADH-type hydrogenation reaction for possible CO 2  reduction using the NAD + /NADH redox function has been constructed.

A Novel Photo-Driven Hydrogenation Reaction of an NAD+-Type Complex Toward Artificial Photosynthesis