Enhanced Photo-Electrochemical Responses through Photo-Responsive Ruthenium Complexes on ITO Nanoparticle Surface

The mononuclear ruthenium 1-Cl and dinuclear ruthenium 2-Cl complexes undergo a photo-induced ligand exchange in water, affording the corresponding 1-H2O and 2-H2O complexes. The use of indium tin oxide nanoparticles (nanoITOs) to explore the photo-electrochemistry of the in situ-generated 1-H2O and 2-H2O in solution revealed greater photocurrents produced by these two complexes when compared with an experiment using a buffer only. Interestingly, the high photocurrent shown by the dinuclear complex 2-H2O was accompanied by the deposition of its higher oxidation state (H2O)Ru-II-Ru-III(OH), as evidenced with cyclic voltammetry, SEM and XPS. The IPCE and spectro-electrochemistry studies supported by TD-DFT calculations revealed the visible light harvesting ability of 1-H2O and 2-H2O in solution and the subsequent electron injection into the conduction band of the nanoITOs, enhanced in 2-H2O via a plausible chelating effect.