Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster.

Hydrogen-atom (H-atom) transfer at the surface of heterogeneous metal oxides has received significant attention owing to its relevance in energy conversion and storage processes. Here, we present the synthesis and characterization of an organofunctionalized polyoxovanadate cluster, (calix)VO(OH)(OMe) (calix = 4--butylcalix[4]arene). Through a series of equilibrium studies, we establish the BDFE(O-H) of the aquo ligand as 62.