Computational Study on the Light-Induced Oxidation of Iridium-Aqua Complex to Iridium-Oxo Complex over WO3(001) Surface.

An iridium aqua complex [IrIII(η5-C5Me5){bpy(COOH)2}(H2O)]2+ under visible light irradiation has been experimentally reported to form an iridium–oxo (Ir–oxo) complex [IrV(η5-C5Me5){bpy(COOH)2}(O)]2+, which oxidizes H2O to O2. However, the mechanism for the formation of this Ir–oxo complex remains unclear, due to the difficulties in observing the unstable Ir–oxo complex and computing light-induced systems having different numbers of electrons. In this study, we perform density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to investigate more in detail our previously proposed deprotonation and light-induced oxidation reactions composing the formation of the Ir–oxo complex. In particular, we discuss effects of light irradiation and WO3 support on the formation of the Ir–oxo complex. We suggest two distinct mechanisms, that is, direct and indirect for the light-induced oxidation. In the direct mechanism electrons are directly transferred from the occupied π* orbitals of IrIII–OH or IrIV...