Charge-State Dependence of Proton Uptake in Polyoxovanadate-alkoxide Clusters

[Image: see text] Here, we present an investigation of the thermochemistry of proton uptake in acetonitrile across three charge states of a polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V(6)O(7)(OMe)(12)](n) (n = 2–, 1–, and 0). The vanadium oxide assembly studied features bridging sites saturated by methoxide ligands, isolating protonation to terminal vanadyl moieties. Exposure of [V(6)O(7)(OMe)(12)](n) to organic acids of appropriate strength results in the protonation of a terminal V=O bond, generating the transient hydroxide-substituted POV-alkoxide cluster [V(6)O(6)(OH)(OMe)(12)](n+1). Evidence for this intermediate proved elusive in our initial report, but here we present the isolation of a divalent anionic cluster that features hydrogen bonding to dimethylammonium at the terminal oxo site. Degradation of the protonated species results in the formation of equimolar quantities of one-electron-oxidized and oxygen-atom-efficient complexes, [V(6)O(7)(OMe)(12)](n+1) and [V(6)O(6)(OMe)(12)](n+1). While analogous reactivity was observed across the three charge states of the cluster, a dependence on the acid strength was observed, suggesting that the oxidation state of the vanadium oxide assembly influences the basicity of the cluster surface. Spectroscopic investigations reveal sigmoidal relationships between the acid strength and cluster conversion across the redox series, allowing for determination of the proton affinity of the surface of the cluster in all three charge states. The fully reduced cluster is found to be the most basic, with higher oxidation states of the assembly possessing substantially reduced proton affinities (∼7 pK(a) units per electron). These results further our understanding of the site-specific reactivity of terminal M=O bonds with protons in an organic solvent, revealing design criteria for engineering functional surfaces of metal oxide materials of relevance to energy storage and conversion.