In situ spectroscopic characterization of a solution-phase X-type ligand exchange at colloidal lead sulphide quantum dot surfaces.

We employed quantitative NMR spectroscopy and spectrophotometric absorbance titration to study a quantum dot X-type ligand exchange reaction. We find that the exchange is highly cooperative, where at low extents of exchange the change in free energy of the reaction, ΔGXC, is ∼11 kJ mol-1 while at higher extents of exchange ΔGXC saturates to ∼-4 kJ mol-1. A modified Fowler binding isotherm is developed to describe the reaction.