Supramolecular confinement effect enabling light-harvesting system for photocatalytic α-oxyamination reaction  

作　　者：Xuanyu Wang Zhao Gao Wei Tian 

机构地区：[1]Shaanxi Key Laboratory of Macromolecular Science and Technology,Xi'an Key Laboratory of Hybrid Luminescent Materials and Photonic Device,MOE Key Laboratory of Material Physics and Chemistry under Extraordinary Conditions,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi'an 710072,China

出　　处：《Chinese Chemical Letters》2024年第11期309-313,共5页中国化学快报（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos.22371230,22022107,22001213,and 22071197);the Postdoctoral Science Foundation of China (Nos.2023M732855,2022TQ0258);the Shaanxi Fundamental Science Research Project for Chemistry & Biology (No.22JHQ020)。

摘　　要：The supramolecular F?rster resonance energy transfer(FRET)is seen as a promising approach for organic photocatalysis using dyes as catalysts,because it combines the high efficiency of energy transfer with the dynamic responsiveness based on non-covalent interactions.Here we propose a supramolecular FRET photocatalysis strategy forα-oxyamination reaction based on supramolecular confinement effect.The well-designed benzothiadiazole-based cationic monomer as energy donor and the dyes of Nile Red as acceptor are doped into the amphiphilic surfactants of sodium dodecyl sulfate(SDS).Benefitting from the supramolecular confinement space provided by SDS in aqueous environment,the FRET process between the monomer and Nile Red is effectively achieved(exciton migration rate:3.99×10^(14)L mol^(-1)s^(-1)).On this basis,the supramolecular FRET system is used as an efficient energy source to catalyzeα-oxyamination reactions between a series of 1,3-dicarbonyl compounds and 2,2,6,6-tetramethylpiperidine-1-oxyl under white LED light,showing a yield as high as 94%and a turnover frequency value of 3.92 h^(-1).This photocatalytic result shows a great enhancement compared to that of Nile Red alone.

关 键 词：Self-assembly Supramolecular chemistry Light harvesting Energy transfer Confinement effect 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学] O621.251