Publication date: 15th May 2025
Quantum dots (QDs) are highly promising photoredox catalysts due to their tunable redox potentials, broad absorption spectra, and superior photostability compared to organic or precious metal-based photocatalysts. Previous studies have demonstrated their utility in various organic transformations, including dehalogenations, C–C bond formations, and the reduction of nitrobenzene to aniline.¹ Despite their potential, one of the most commonly used QDs—cadmium sulfide (CdS)—suffers from photodegradation caused by surface cadmium reduction.2 Although coating CdS with a ZnS shell improves photostability, it often comes at the expense of reduced catalytic efficiency. In this work, we investigate Mn²⁺-doped CdS/ZnS quantum dots, which exhibit enhanced reducing power due to Auger upconversion that generates hot electrons capable of long-range electron transfer.3 Compared to undoped CdS QDs, the Mn²⁺-doped CdS/ZnS QDs show improved photostability and a modest increase in reaction yield when used with carboxylate ligands in a non-polar environment. Notably, exchanging the native stearate ligands on Mn²⁺-doped CdS/ZnS QDs with more polar ligands—such as 3-mercaptopropionic acid (MPA), 3-phosphonopropionic acid (PPA), and tributylammonium formate (TBAF)—significantly enhances the yield of dechlorination reactions at very low catalyst loadings. These improvements occur while retaining Mn²⁺ emission after reaction (in the case of PPA-capped dots) and achieving superior reducing power with TBAF-capped dots.
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