Bis-Cyclometalated Iridium Complexes Containing 4,4a?2-Bis(phosphonomethyl)-2,2a?2-bipyridine Ligands: Photophysics, Electrochemistry, and High-Voltage Dye-Sensitized Solar Cells

摘要： In this report, the synthesis and characterization of two bis-cyclometalated iridium(III) complexes are presented. Single-crystal X-ray diffraction shows [Ir(ppy)2(4,4′-bis(diethylphosphonomethyl)-2,2′-bipyridine)]PF6 adopts a pseudo-octahedral geometry. The complexes have an absorption feature in the near-visible?UV region and emit green light with excited-state lifetimes in hundreds of nanoseconds. The redox properties of these complexes show reversible behavior for both oxidative and reductive events. [Ir(ppy)2(4,4′-bis(phosphonomethyl)-2,2′-bipyridine)]PF6 readily binds to metal oxide supports, like nanostructured SnIV-doped In2O3 and TiO2, while still retaining reversible redox chemistry. When incorporated as the photoanode in dye-sensitized solar cells, the devices exhibit open-circuit voltages of >1 V, which is a testament to their strength of these iridium(III) complexes as photochemical oxidants.