Self-Assembled Bilayers on Nanocrystalline Metal Oxides: Exploring the Non-Innocent Nature of the Linking Ions

Self-assembled bilayers on nanocrystalline metal oxide films are an increasingly popular strategy for modulating electron and energy transfer at dye-semiconductor interfaces. A majority of the work to date has relied on Zr^II and Zn^IV linking ions to assemble the films. In this report, we demonstrate that several different cations (Cd^II, Cu^II, Fe^II, La^III, Mn^II, and Sn^IV) are not only effective in generating the bilayer assemblies but also have a profound influence on the stability and photophysical properties of the films. Bilayer films with Zr^IV ions exhibited the highest photostability on both TiO₂ and ZrO₂. Despite the metal ions having a minimal influence on the absorption/emission energies and oxidation potentials of the dye, bilayers composed of Cu^II, Fe^II, and Mn^II exhibit significant excited-state quenching. The excited-state quenching decreases the electron injection yield but also, for Cu^II and Mn^II bilayers, significantly slows the back electron transfer kinetics.