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Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots
Author(s) -
Li XuBing,
Li ZhiJun,
Gao YuJi,
Meng QingYuan,
Yu Shan,
Weiss Richard G.,
Tung ChenHo,
Wu LiZhu
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310249
Subject(s) - quantum dot , chemistry , reagent , photochemistry , catalysis , photocatalysis , combinatorial chemistry , nanotechnology , visible spectrum , materials science , organic chemistry , optoelectronics
Abstract Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H 2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.