Physicochemical implications of surface alkylation of high-valent, Lindqvist-type polyoxovanadate-alkoxide clusters
Alex A. Fertig, S. M. Gulam Rabbani, Melissa D. Koch, William W. Brennessel, Pere Miró, Ellen M. Matson
Abstract
, respectively. Comparison of the electronic absorption spectra of the functionalised and unfunctionalised derivatives indicates the decreased overall charge of the complex results in a decrease in the energy required for ligand to metal charge transfer events to occur, while simultaneously mitigating the inductive effects imposed by the capping TRIOL ligand. Electrochemical analysis of the family of organofunctionalised polyoxovanadate clusters reveals the relationship of ligand environment and the redox properties of the cluster core: increased organofunctionalisation of the surface of the vanadium oxide assembly translates to anodic shifts in the reduction events of the Lindqvist ion. Overall, this work provides insight into the electronic effects induced upon atomically precise modifications to the surface structure of nanoscopic, redox-active metal oxide assemblies.