Tailorable Multi-Photoresponsive Behavior Triggered by Different Sulfur Oxidation States  

作　　者：Jingjing Guo Xiaoluo Peng Shihuai Wang Shuai Bi Ting He Yu Cheng Zujin Zhao Ben Zhong Tang Yanli Zhao 

机构地区：[1]School of Chemistry,Chemical Engineering and Biotechnology,Nanyang Technological University,Singapore 637371 [2]State Key Laboratory of Luminescent Materials and Devices,Key Laboratory of Luminescence from Molecular Aggregates of Guangdong Province,South China University of Technology,Guangzhou 510640 [3]School of Science and Engineering,The Chinese University of Hong Kong,Shenzhen,Guangdong 518172

出　　处：《CCS Chemistry》2024年第10期2465-2475,共11页中国化学会会刊（英文）

基　　金：supported by the Agency for Science,Technology and Research Singapore through its Manufacturing,Trade and Connectivity Individual Research Grant(grant no.M22K2c0077);the National Natural Science Foundation of China(grant nos.21788102,22375066,21874121,and 21974128);the Guangdong Basic and Applied Basic Research Foundation(grant nos.2023B1515040003 and 2022A1515010315).

摘　　要：Photoresponsive materials are considered as promising systems for intelligent technology applications owing to the contactless spatial and temporal control.Herein,controllable multi-photoresponsive behaviors are realized in benzo[b]thiophene derivatives(o-DMP-S,o-DMP-SO,and o-DMP-SO_(2))by modulating the sulfur oxidation state.Among them,o-DMP-S is photo-unreactive but possesses denser molecular packing upon ultraviolet(UV)light irradiation,exhibiting photoenhanced room-temperature phosphorescence properties.Through stoichiometric oxidation of the sulfur atom in o-DMP-S,the resulting sulfoxide compound o-DMP-SO undergoes a radical photolysis reaction involving photodeoxygenation and photochemical rearrangement,thereby leading to the photomechanical effect.The sulfone compound o-DMP-SO_(2)displays prominent reversible photochromism,resulting from the radical photocyclization under 365 nm UV light irradiation.Based on comprehensive experimental and computational investigations,the diverse photoresponsive behaviors of these benzo[b]thiophene derivatives are demonstrated to depend on the intersystem crossing efficiency and radical-mediated photochemical reaction activity in excited states due to the different sulfur oxidation states.This work provides an insightful understanding of the relationship between molecular structure and photoresponsive behavior and opens up the opportunity for the development of photoresponsive materials with potential applications.

关 键 词：photoenhanced room-temperature phosphorescence photomechanical effect radicalmediated photochemical reaction reversible photochromism sulfur oxidation state 

分 类 号：O62[理学—有机化学]