Wang Shuxin, Tang Li, Cai Baogui, Yin Zhengmao, Li Yangfeng, Xiong Lin, Kang Xi, Xuan Jun, Pei Yong, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui University, Hefei, Anhui 230601, China.
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, Shandong 266042, China.
J Am Chem Soc. 2022 Mar 9;144(9):3787-3792. doi: 10.1021/jacs.2c01570. Epub 2022 Feb 28.
The inorganic-organic interface between metal catalysts and their substrates greatly influences reaction processes, but few studies of this interface have been conducted for a detailed understanding of its structure. Herein, we describe the synthesis and structural determination of an arylthiolated Au(F-Ph) nanocluster and characterize in detail the key roles of its ligands in photocatalyzed oxidative functionalization reactions. The most significant findings are that (i) interactions are established between ligands to avoid distortion of the geometric structure, limit the Jahn-Teller effect, and protect the nanocluster from oxidization and (ii) the low energy gap (HOMO-LUMO) of the synthetic clusters enables three types of photocatalytic oxidative functionalization reactions by near-infrared light (850 nm).
金属催化剂与其底物之间的无机-有机界面极大地影响反应过程，但针对该界面进行的详细结构研究却很少。在此，我们描述了芳基硫醇化金（F-Ph）纳米团簇的合成与结构测定，并详细表征了其配体在光催化氧化官能团化反应中的关键作用。最重要的发现是：（i）配体之间建立了相互作用，以避免几何结构变形、限制 Jahn-Teller 效应并保护纳米团簇不被氧化；（ii）合成团簇的低能隙（最高占据分子轨道-最低未占据分子轨道）使得通过近红外光（850 nm）能够进行三种类型的光催化氧化官能团化反应。
