AbstractCdSe quantum dots (QDs) with several different ligands were prepared by ligand exchange reactions of trioctylphosphine oxide (TOPO)/trioctylphosphine selenide (TOPSe) passivated QDs with an excess of new ligands, such as pyridine, 4-picoline, thiophenol, 4-(trifluoromethyl)-thiophenol, and tris(2-ethylhexyl)phosphate. We find that 85–90% of ligands passivating the surface of the QDs are the newly introduced capping species and 10–15% are native TOPO/TOPSe ligands, reflecting the incomplete exchange of the QD surface. Thermal gravimetric analysis (TGA) and quantitative proton NMR measurements show that on average only 30% of surface cadmium atoms are passivated by TOPO/TOPSe. Approximately 1/3 of these native ligands occupy sites too strongly bound to be replaced by ligand exchange reactions.
Post-synthetic ligand exchange modulates the absorbance and emission energies of colloidal CdSe quantum dots
