Architecture of supramolecular metal complexes for photocatalytic CO2 reduction:: Ruthenium-rhenium bi- and tetranuclear complexes

We study the electrochemical, spectroscopic, and photocatalytic properties of a series of Ru(II)-Re(I) binuclear complexes linked by bridging ligands 1,3-bis(4 '-methyl-[2,2 ']bipyridinyl-4-yl)propan-2-ol (bpyC(3)bpy) and 4-methyl-4 '-[1,10]phenanthroline-[5,6-d]imidazol-2-yl)bipyridine (mfibpy) and a tetranuclear complex in which three [Re(CO)(3)Cl] moieties are coordinated to the central Ru using the bpyC(3)bpy ligands. In the bpyC(3)bpy binuclear complexes, 4,4 '-dimethyl-2,2 '-bipyridine (dmb) and 4,4 '-bis(trifluoromethyl)-2,2 '-bipyridine ({CF3}(2)bpy), as well as 2,2 '-bipyridine (bpy), were used as peripheral ligands on the Ru moiety. Greatly improved photocatalytic activities were obtained only in the cases of [Ru{bpyC(3)bpyRe(CO)(3)Cl}(3)](2+) (RuRe3) and the binuclear complex [(dmb)(2)Ru(bpyC(3)bpy)Re-(CO)(3)Cl](2+) (d(2)Ru-Re), while photocatalytic responses were extended further into the visible region. The excited state of ruthenium in all Ru-Re complexes was efficiently quenched by 1-benzyl-1,4-dihydronicotinamide (BNAH). Following reductive quenching in the case of d(2)Ru-Re, generation of the one-electron-reduced (OER) species, for which the added electron resides on the Ru-bound bpy end of the bridging ligand bpyC(3)bpy, was confirmed by transient absorption spectroscopy. The reduced Re moiety was produced via a relatively slow intramolecular electron transfer, from the reduced Ru-bound bpy to the Re site, occurring at an exchange rate (Delta G similar to 0). Electron transfer need not be rapid, since the rate-determining process is reduction Of CO2 with the OER species of the Re site, Comparison of these results with those for other bimetallic systems gives us more general architectural pointers for constructing supramolecular photocatalysts for CO2 reduction.