biostudies-literatureCogan NMBBasic Energy Sciences10221-10227https://www.ebi.ac.uk/biostudies/studies/S-EPMC10683070biostudies-literatureUnknown23(22)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 <i>ex situ</i> 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.Nano lettersEfficient Hole Transfer from CdSe Quantum Dots Enabled by Oxygen-Deficient Polyoxovanadate-Alkoxide Clusters.PMC10683070DE-SC0002106McClelland KPMatson EMAmin MPeter CYMCogan NMBCarmenate Rodriguez CKrauss TDBrennessel WWFertig AAfalseEfficient 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 <i>ex situ</i> 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.2023-01-01T00:00:00Z2023 Nov2025-04-18T13:12:59.617Z2025-04-06T22:46:14.391ZS-EPMC106830703793502210.1021/acs.nanolett.3c02749