Ruthenium Picolinate Complex as a Redox Photosensitizer With Wide-Band Absorption.

Ruthenium(II) picolinate complex, [Ru(dmb)2(pic)](+) (Ru(pic); dmb = 4,4'-dimethyl-2,2'-bipyridine; Hpic = picolinic acid) was newly synthesized as a potential redox photosensitizer with a wider wavelength range of visible-light absorption compared with [Ru((NN)-N-boolean AND)(3)](2+) ((NN)-N-boolean AND = diimine ligand), which is the most widely used redox photosensitizer. Based on our investigation of its photophysical and electrochemical properties, Ru(pic) was found to display certain advantageous characteristics of wide-band absorption of visible light (lambda(abs) < 670 nm) and stronger reduction ability in a one-electron reduced state (E-1/2(red) = -1.86 V vs. Ag/AgNO3), which should function favorably in photon-absorption and electron transfer to the catalyst, respectively. Performing photocatalysis using Ru(pic) as a redox photosensitizer combined with a Re(I) catalyst reduced CO2 to CO under red-light irradiation (lambda(ex) > 600 nm). TONCO reached 235 and Phi(CO) was 8.0%. Under these conditions, [Ru(dmb)(3)](2+) (Ru(dmb)) is not capable of working as a redox photosensitizer because it does not absorb light at lambda > 560 nm. Even in irradiation conditions where both Ru(pic) and Ru(dmb) absorb light (lambda(ex) > 500 nm), using Ru(pic) demonstrated faster CO formation (TOFCO = 6.7 min(-1)) and larger TONCO (2347) than Ru(dmb) (TOFCO = 3.6 min(-1); TONCO = 2100). These results indicate that Ru(pic) is a superior redox photosensitizer over a wider wavelength range of visible-light absorption.