Chemical and photochemical functionality of the first molecular bismuth vanadium oxide

Anionic metal oxide clusters, so-called polyoxometalates, can be developed as molecular model compounds to mimic the chemical and photochemical reactivity of solid-state metal oxides on the molecular level. Inspired by the well-known visible-light photocatalyst BiVO(4), the first molecular bismuth vanadium oxide has been synthesized to investigate the chemical and photochemical similarities between the solid-state and molecular compounds. The cluster H(3)[(Bi(dmso)(3))(4)V(13)O(40)]·ca. 4 DMSO was obtained from simple precursors in almost quantitative yield. Structural analysis showed that the cluster shell is based on the unusual all-vanadium ε-Keggin framework [ε-V(12)O(40)](15-), which is stabilized by coordination of four Bi(III) centers. The acidic character of the three cluster protons was demonstrated by titration studies. The cluster shows promising photocatalytic properties in visible-light photooxidation reactions and has high activity (turnover number >1200), high quantum yield (Φ=7.6 %), and good recyclability, which make it a promising first example of a new class of heterometallic polyoxometalates.