Control of the Redox Activity of Quantum Dots through Introduction of Fluoroalkanethiolates into Their Ligand Shells

Increasing the fraction of 1H,1H,2H,2H-perfluorodecanethiol (PFDT) in the mixed-PFDT/oleate ligand shell of a PbS quantum dot (QD) dramatically reduces the permeability of the ligand shell to alkyl-substituted benzoquinones (s-BQs), as measured by a decrease in the efficiency of collisional photoinduced electron transfer. Replacing only 21% of the oleates on the QD surface with PFDT reduces the yield of photo-oxidation by tetramethyl BQ by 68%. Experiments with s-BQ quenchers of two different sizes reveal that the degree of protection provided by the PFDT-doped monolayer, relative to a decanethiolate (DT)-doped monolayer at similar coverage, is due to both size exclusion (PFDT is larger and more rigid than DT), and the oleophobicity of PFDT. This work demonstrates the usefulness of fluorinated ligands in designing molecule-selective and potentially corrosion-inhibiting surface coatings for QDs for applications as robust emitters or high fidelity sensing platforms.