Modulating Hole Transfer from CdSe Quantum Dots by Manipulating the Surface Ligand Density
Hannah Gorski a, Chari Y. M. Peter a, Chayan Carmenate Rodriguez a, Elizabeth O. Phinney a
a University of Rochester, 120 Trustee Road, Rochester, New York, 14534, United States
Poster, Hannah Gorski, 073
Publication date: 15th May 2025

The structure and density of surface capping ligands in cadmium chalcogenide
quantum dots (QDs) are important considerations for controlling the efficiency of charge
separation via the transfer of electrons or holes to molecular acceptors. Here we show how
the manipulation of the surface ligand density of oleic acid-capped cadmium selenide (CdSe) QDs impacts the efficiency of hole transfer (HT) to polyoxovanadate alkoxides. Meerwein’s salt is used as a ligand-stripping agent, providing opportunities to quantitatively manipulate the ligand density at the surface of the nanocrystal, as evidenced by 1H NMR spectroscopy. Time-resolved photoluminescence and transient absorption spectroscopies reveal that the extent of HT is quantitatively related to increased surface accessibility. Collectively, these results show that the reduction of surface ligand density can be used to tune the extent of interactions of molecular acceptors with QDs, providing a route to control charge-transfer processes relevant to improving the efficiency of QDs as photosensitizers.

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