Novel ruthenium bipyridyl dyes with S-donor ligands and their application in dye-sensitized solar cells

Two series of novel ruthenium bipyridyl dyes incorporating sulfur-donor bidentate ligands with general formula [Ru(R-bpy)2C2N2S2] and [Ru(R-bpy)2(S2COEt)][NO3] (where R = H, CO2Et, CO2H; C2N2S2 = cyanodithioimidocarbonate and S2COEt = ethyl xanthogenate) have been synthesized and characterized spectroscopically, electrochemically and computationally. The acid derivatives in both series (C2N2S2 3 and S2COEt 6) were used as a photosensitizer in a dye-sensitized solar cell (DSSC) and the incident photo-to-current conversion efficiency (IPCE), overall efficiency (η) and kinetics of the dye/TiO2 system were investigated. It was found that 6 gave a higher efficiency cell than 3 despite the latter dyeʹs more favorable electronic properties, such as greater absorption range, higher molar extinction coefficient and large degree of delocalization of the HOMO. The transient absorption spectroscopy studies revealed that the recombination kinetics of 3 were unexpectedly fast, which was attributed to the terminal CN on the ligand binding to the TiO2, as evidenced by an absorption study of R = H and CO2Et dyes sensitized on TiO2, and hence leading to a lower efficiency DSSC.