文献类型：期刊文献

英文题名：Enhancing tetraphenylethene cyclization as photoswitch

作者：Wu, Yue[1];Ren, Yiran[1];Zeng, Xiaoxuan[1];Hu, Honglong[2,3];Li, Mengqi[2,3];Li, Junzi[4];He, Tingchao[4];Li, Xin-Shun[1];Yu, Zhen-Qiang[1];Zhu, Wei-Hong[2,3]

机构：[1]Shenzhen Univ, Coll Chem & Environm Engn, Shenzhen, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Lab Adv Mat,Inst Fine Chem,Feringa Nobel Prize Sci, Shanghai, Peoples R China;[3]East China Univ Sci & Technol, Inst Fine Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Inst Fine Chem,Feringa Nobel Prize Scientist Joint, Shanghai, Peoples R China;[4]Shenzhen Univ, Coll Phys & Optoelect Engn, Key Lab Optoelect Devices & Syst, Minist Educ & Guangdong Prov, Shenzhen, Peoples R China

年份：2023

卷号：1

期号：2

外文期刊名：SMART MOLECULES

收录：WOS:【ESCI(收录号:WOS:001498807800001)】；

基金：This work was supported by NSFC/China (21788102, 21636002, 21622602, 21875143, 21908146, and 21908060), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), Innovation Program of Shanghai Municipal Education Commission, Scientific Committee of Shanghai (15XD1501400), Programme of Introducing Talents of Discipline to Universities (B16017), China Postdoctoral Science Foundation (2019M651417), and Innovation Research Foundation of Shenzhen (JCYJ20180507182229597).

语种：英文

外文关键词：aggregation-induced emission; diarylethene; photocyclization; photoswitch; tetraphenylethene

摘要：Tetraphenylethene (TPE), a star building block with promising aggregation-induced emission, has received much interest. Given that its intramolecular Woodward-Hoffmann cyclic intermediate instantaneously converts back to the original state within several picoseconds, the essentially photochromic characteristic of TPE is little investigated. Achieving a visible photocyclization of TPE is still an unsolved issue and considered as the bottleneck in the further advancement of applications. We report a strategy of attaching carbonate ester onto the TPE skeleton (TPE-4C) to enhance TPE photocyclization stability. As demonstrated, the incorporated cholesteryloxycarbonyloxy substituents in TPE-4C can increase the energy barrier for cycloreversion, thereby exhibiting extremely thermal stability of photocyclic intermediate upon UV irradiation, prolonging its lifetime from 63 picoseconds to 46 s by 7.2 x 1011-fold. The photoinduced cyclization of TPE-4C could be monitored with naked eyes, and the photocyclization/cycloreversion is achieved by turning on/off UV light along with a relative fatigue resistance. Encapsulation of TPE-4C into the liquid crystal can induce a striking phase transformation (achiral <-> chiral), which can be applicable to encode optical information. Employing carbonate ester into the TPE unit plays a vital role in enhancing the unprecedented TPE photocyclization stability, providing a toolbox to allow TPE-based photocyclization to be visually monitored.