Light-Controlled Switch for Divergent Coupling of Thiols to Disulfides/Thioethers over CdS Quantum Dots

IF 8.7 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY ACS Materials Letters Pub Date : 2025-03-24 DOI:10.1021/acsmaterialslett.5c00142

Ming-Yu Qi, Xin-Ni Shao, Zi-Rong Tang* and Yi-Jun Xu*,

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Abstract

Switchable divergent organic transformations represent a straightforward but challenging method to synthesize structurally varied compounds starting from the same set of raw materials. Herein, we report the divergent dehydrocoupling of thiols into tunable disulfides/thioethers and H₂ in response to the visible or ultraviolet (UV) light, over CdS quantum dots. Regulating the irradiation wavelength allows disulfides and thioethers to be synthesized in moderate to high yields with good functional group tolerance. Mechanistic studies reveal that thiols are oxidized to produce sulfur-centered radicals by photogenerated holes under visible light irradiation, which then undergo S–S coupling to form disulfides. While under UV light irradiation, the cleavage of C–S bonds in thiols occurs readily to afford aryl radicals, which interact with sulfur-centered radicals, undergoing C–S coupling to obtain thioethers. This work is expected to open an avenue of light-controlled switch to maneuver a radical conversion route for divergent synthesis of value-added fine chemicals.

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CdS量子点上硫醇到二硫化物/硫醚发散耦合的光控开关

可切换的发散有机转化是一种简单但具有挑战性的方法，可以从同一组原料合成结构不同的化合物。在此，我们报道了硫醇在可见光或紫外线（UV）光下在CdS量子点上发散脱氢偶联成可调的二硫化物/硫醚和H2。调节辐照波长可使二硫化物和硫醚以中高收率合成，并具有良好的官能团耐受性。机理研究表明，在可见光照射下，硫醇通过光生空穴被氧化生成以硫为中心的自由基，然后发生S-S耦合形成二硫化物。而在紫外光照射下，硫醇中的C-S键很容易发生裂解，从而产生芳基自由基，芳基自由基与硫中心自由基相互作用，发生C-S偶联得到硫醚。这项工作有望开辟光控开关的途径，以操纵自由基转化路线的发散合成增值精细化学品。

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来源期刊

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.