Efficient Light-to-Electrical Energy Conversion with Dithiocarbamate−Ruthenium Polypyridyl Sensitizers

Abstract
New Ru(dcbH)(dcbH2)(L) sensitizers, where L is diethyldithiocarbamate, dibenzyldithiocarbamate, or pyrrolidinedithiocarbamate, dcbH is 4-(COOH)-4‘-(COO-)-2,2‘-bipyridine, and dcbH2 is 4,4‘-(COOH)2-2,2‘-bipyridine, have been synthesized, characterized, and anchored to nanocrystalline TiO2 films for light to electrical energy conversion in regenerative photoelectrochemical cells with I-/I2 acetonitrile electrolyte. The sensitizers have intense metal-to-ligand charge-transfer (MLCT) bands centered ∼380 and 535 nm that sensitize TiO2 over a notably broad spectral range. The photophysical and photoelectrochemical studies of these materials are contrasted with cis-Ru(dcbH2)2(NCS)2, which is one of the most efficient sensitizers reported to date. Photophysical measurements show that the high photocurrent observed for cis-Ru(dcb)2(NCS)2/TiO2 is due to efficient and rapid iodide oxidation.

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