The chemical environments of oleate species within samples of oleate-coated PbS quantum dots

A combination of FT-IR, (1)H NMR, nuclear Overhauser effect (NOESY), and diffusion-ordered (DOSY) NMR spectroscopies shows that samples of oleate-coated PbS quantum dots (QDs) with core radii ranging from 1.6 to 2.4 nm, and purified by washing with acetone, contain two species of oleate characterized by the stretching frequencies of their carboxylate groups, the chemical shifts of their protons, and their diffusion coefficients. One of these oleate species exists primarily on the surfaces of the QDs and either chelates a Pb(2+) ion or bridges two Pb(2+) ions. The ratio of bridging oleates to chelating oleates on the surfaces of the QDs is approximately 1:1 for all sizes of the QDs we studied. The second oleate species in these samples bridges two Pb(2+) ions within clusters or oligomers of lead oleate (with a hydrodynamic radius of ~1.4 nm), which are byproducts of the QD synthesis. The concentration of these clusters increases with increasing size of the QDs because larger QDs are produced by increasing the concentration of the oleic acid ligand in the reaction mixture. The oleate molecules on the surfaces of the QDs and within the lead oleate clusters are in rapid exchange with each other. Additional washes with methanol progressively eliminate the contaminating clusters from the PbS QD samples. This work quantitatively characterizes the distribution of binding geometries at the inorganic/organic interface of the nanocrystals and demonstrates the utility of using organic ligands as probes for the composition of a colloidal QD sample as a function of the preparation procedure.