Chalcogenol Ligand Toolbox for CdSe Nanocrystals and Their Influence on Exciton Relaxation Pathways

We have employed a simple modular approach to install small chalcogenol ligands on the surface of CdSe nanocrystals. This versatile modification strategy provides access to thiol, selenol, and tellurol ligand sets <i>via</i> the <i>in situ</i> reduction of R₂E₂ (R = ^<i>t</i>Bu, Bn, Ph; E = S, Se, Te) by diphenylphosphine (Ph₂PH). The ligand exchange chemistry was analyzed by solution NMR spectroscopy, which reveals that reduction of the R₂E₂ precursors by Ph₂PH directly yields active chalcogenol ligands that subsequently bind to the surface of the CdSe nanocrystals. Thermogravimetric analysis, FT-IR spectroscopy, and energy dispersive X-ray spectroscopy provide further evidence for chalcogenol addition to the CdSe surface with a concomitant reduction in overall organic content from the displacement of native ligands. Time-resolved and low temperature photoluminescence measurements showed that all of the phenylchalcogenol ligands rapidly quench the photoluminescence by hole localization onto the ligand. Selenol and tellurol ligands exhibit a larger driving force for hole transfer than thiol ligands and therefore quench the photoluminescence more efficiently. The hole transfer process could lead to engineering long-lived, partially separated excited states