Publication date: 22nd July 2026
Colloidal quantum dots (QDs) have revealed promises as triplet sensitizers for organic reactions in place of conventional homogeneous catalysts.[1,2] QDs triplet sensitizers are commonly functionalized with a molecular dye to form QD/dye hybrids.[3,4] The dye is believed to serve as both energy shuttle and non-covalent binding site for the freely diffusing substrate, overcoming the physical barrier imposed by the native ligands shell.[5] Yet, fundamental understanding of the impact that QDs surface ligands have in a triplet sensitized system is lacking, hampering the full exploitation of their potential. In this contribution, we look at the surface chemistry of low-toxicity ZnSe QDs and we investigate the role of native ligands in mediating the interaction and sensitization of organic substrates without relying on molecular dyes. We show that the dynamicity of ligands allows for the direct QD-substrate interaction. Furthermore, we observe that the presence of a dipole moment in the substrate favors the dynamic exchange with native ligands on the surface, resulting in a stronger QDs quenching. Finally, we test dye-free ZnSe QDs as sensitizers in the [2+2] cycloaddition of carbonyls. This work highlights the importance that QDs surface chemistry holds in triplet sensitization, as the dynamicity of ligands is found to not hamper the interaction with substrates. We envision that the surface can be exploited as an intrinsic binding site and ligands can be engineered instead of relying on the use of molecular dyes.
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