Hydrophilic, Hole-Delocalizing Ligand Shell to Promote Charge Transfer from Colloidal CdSe Quantum Dots in Water

Colloidal cadmium chalcogenide nanocrystals are usually stabilized in polar solvents by functionalizing the surface with a layer of hydrophilic ligands. While these ligands protect against aggregation, they also present a steric barrier that hinders surface access. In applications that require charge transfer to and from nanocrystals, colloidal stability and surface access for redox species are therefore difficult to reconcile. This work assesses the possibility of a more dynamic ligand shell that not only provides stability to nanocrystals but also promotes charge transfer without the need for ligand removal. We use transient absorption spectroscopy to study CdSe quantum dots functionalized with hydrophilic, hole-delocalizing dithiocarbamate ligands in water for the first time, and find that a conjugated ligand facilitates charge transfer to redox species in solution.