Controlling the Electronic Coupling between CdSe Quantum Dots and Thiol Capping Ligands via pH and Ligand Selection

Comparison of the UV–vis absorption spectra of CdSe quantum dots (QDs) capped with various mercaptocarboxylic acid capping ligands reveals that only 4-mercaptobenzoic acid (MBzA) capping ligands lower the apparent optical band gap. We propose that the delocalization of the excitons in the CdSe QDs is extended onto the ligands via electronic coupling to the π system of the 4-mercaptobenzoic acid molecules through the Cd–S bond. Furthermore, we demonstrate that the electronic coupling between the QDs and the (MBzA) thiol ligands is influenced by the strength of the Cd–S bond that can be changed by protonating the S atom.