Persistent radical anion of perylene dianhydride:an emerging metal-free photocatalyst for near-infrared photocontrolled RAFT polymerization  

作　　者：Haitao Zhao Guoqing Bian Xiang Xu Weiwei He Lifen Zhang Zhenping Cheng 

机构地区：[1]State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials,Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application,Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,215123,China

出　　处：《Science China Chemistry》2024年第2期677-686,共10页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (21871201);the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。

摘　　要：Developing a new type of photocatalyst(PC) and catalytic mechanism for near-infrared(NIR) photocontrolled reversibledeactivation radical polymerization(RDRP) system is charming but challenging.Herein,a novel PC of the persistent radical anion(PRA)(possessing the properties of both radical and anion) was developed for NIR photocontrolled reversible additionfragmentation chain transfer(RAFT) polymerization,enabling successful polymerization while gaining a deep insight into the mechanism of photo-induced electron transfer RAFT(PET-RAFT) polymerization.Different from the conventional and wellaccepted reductive quenching(RQ) pathway,in which the radical anion intermediates of PCs(PCs^(·-)) must be generated in an excited state(ES),here,the PRA(3,4,9,10-perylenetetracarboxylic dianhydride radical anion(PTCDA^(·-))) could generate conveniently in situ in the ground state(GS) and subsequently serve as highly efficient PC in the NIR region(740–850 nm).The successful implementation of this strategy elucidates the peculiar role played by light and the real way of electron transfer behaviors.In fact,the transfer of a single electron from PRA to chain transfer agent(CTA) and cleavage of the C–S bonds is a process from ES to GS,rather than always from GS(PCs^(·-)) to GS(CTA) in the RQ pathway as is well known to all.In addition,the excellent spatial-temporal control and powerful penetration ability of the NIR light were also confirmed by this PRAcatalyzed polymerization system.

关 键 词：PHOTOCATALYST persistent radical anion(PRA) near-infrared(NIR)light reversible-deactivation radical polymerization(RDRP) photo-induced electron transfer RAFT(PET-RAFT)polymerization 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]