Manipulating Ligand Density at the Surface of Polyoxovanadate-Alkoxide Clusters

We present the post-synthetic modification of a polyoxovanadate-alkoxide (POV-alkoxide) cluster via the reactivity of its cationic form, [V₆O₇(OCH₃)₁₂]¹⁺, with water. This result indicates that cluster oxidation increases the lability of bridging methoxide ligands, affording a ligand exchange reaction that serves to compensate for the increased charge of the cluster core. This synthetic advance affords the isolation of a series of POV-alkoxide clusters with varying degrees of μ₂-O^2- ligands incorporated at the surface, namely, [V₆O₈(OCH₃)₁₁], [V₆O₉(OCH₃)₁₀], and [V₆O₁₀(OCH₃)₉]. Characterization of the POV-alkoxide clusters is described; changes in the infrared and electronic absorption spectra are consistent with the oxidation of the cluster core. We also examine the consequences of ligand substitution on the redox properties of the series of POV-alkoxide clusters via cyclic voltammetry; decreased alkoxide ligand density translates to a cathodic shift of analogous redox events. Ligand substitution also increases comproportionation constants of the Lindqvist core, indicating electron exchange between vanadium centers is promoted in structures with greater numbers of μ₂-O^2- ligands.