Superior Light-Harvesting Heteroleptic Ruthenium(II) Complexes with Electron-Donating Antennas for High Performance Dye-Sensitized Solar Cells.

Three heteroleptic polypyridyl ruthenium complexes, RC-41, RC-42, and RC-43, with efficient electron-donating antennas in the ancillary ligands were designed, synthesized, and characterized as sensitizers for dye-sensitized solar cell. All the RC dye sensitizers showed remarkable light-harvesting capacity and broadened absorption range. Significantly, RC-43 obtained the lower energy metal-ligand charge transfer (MLCT) band peaked at 557 nm with a high molar extinction coefficient of 27 400 M(-1) cm(-1). In conjunction with TiO2 photoanode of submicrospheres and iodide-based electrolytes, the DSSCs sensitizing with the RC sensitizers, achieved impressively high short-circuit current density (19.04 mA cm(-2) for RC-41, 19.83 mA cm(-2) for RC-42, and 20.21 mA cm(-2) for RC-43) and power conversion efficiency (10.07% for RC-41, 10.52% for RC-42, and 10.78% for RC-43). The superior performances of RC dye sensitizers were attributed to the enhanced light-harvesting capacity and incident-photon-to-current efficiency (IPCE) caused by the introduction of electron-donating antennas in the ancillary ligands. The interfacial charge recombination/regeneration kinetics and electron lifetime were further evaluated by the electrochemical impedance spectroscopy (EIS) and transient absorption spectroscopy (TAS). These data decisively revealed the dependences on the photovoltaic performance of ruthenium sensitizers incorporating electron-donating antennas.