Conversion of Light into Electricity with Trinuclear Ruthenium Complexes Adsorbed on Textured TiO2Films

A series of CN-bridged trinuclear Ru complexes of the general structure [RuL2(μ-(CN)Ru(CN)L2′)2] where L is 2,2′-bipyridine-4,4′-dicarboxylic acid and L′ is 2,2′-bipyridine (1)2,2′-bipyridine-4,4′-dicarboxylic acid (2), 4,4′-dimethyl-2,2′-bipyridine (3), 4,4′-diphenyl-2,2′-bipyridine (4), 1,10-phenanthroline (5), and bathophenanthrolinedisulfonic acid (6) have been synthesized, and their spectral and electrochemical properties investigated. The two carboxylic functions on the 2,2′-bipyridine ligand L serve as interlocking groups through which the dye is attached at the surface of TiO2 films having a specific surface texture. The role of these interlocking groups is to provide strong electronic coupling between the π* orbital of the 2,2′-bipyridine and the 3d-wave-function manifold of the conduction band of the TiO2, allowing the charge injection to proceed at quantum yields close to 100 %. The charge injection and recombination dynamics have been studied with colloidal TiO2, using laser photolysis technique in conjunction with time-resolved optical spectroscopy. Photocurrent action spectra obtained from photo-electrochemical experiments with these trinuclear complexes cover a very broad range in the visible, making them attractive candidates for solar light harvesting. Monochromatic incident photon-to-current conversion efficiencies are strikingly high exceeding 80% in some cases. Performance characteristics of regenerative cells operating with these trinuclear complexes and ethanolic triiodide/iodide redox electrolyte have been investigated. Optimal results were obtained with complex 1 which gave a fill factor of 75 % and a power conversion efficiency of 11.3% at 520 nm.