Efficient Hole Transfer from CdSe Quantum Dots Enabled by Oxygen-Deficient Polyoxovanadate-Alkoxide Clusters

A limitation of the implementation of cadmium chalcogenide quantum dots (QDs) in charge transfer systems is the efficient removal of photogenerated holes. Rapid hole transfer has typically required the ex situ functionalization of hole acceptors with groups that can coordinate to the surface of the QD. In addition to being synthetically limiting, this strategy also necessitates a competitive binding equilibrium between the hole acceptor and native, solubilizing ligands on the nanocrystal. Here we show that the incorporation of oxygen vacancies into polyoxovanadate-alkoxide clusters improves hole transfer kinetics by promoting surface interactions between the metal oxide assembly and the QD. Investigating the reactivity of oxygen-deficient clusters with phosphonate-capped QDs reveals reversible complexation of the POV-alkoxide with a phosphonate ligand at the nanocrystal surface. These findings reveal a new method of facilitating QD-hole acceptor association that bypasses the restrictions of exchange interactions.