Topologically engineering of π-conjugated macrocycles: Tunable emission and photochemical reaction toward multi-cyclic polymers

作     者：Yi Liu Peng Lei Yang Feng Shiwei Fu Xiaoqing Liu Siqi Zhang Bin Tu Chen Chen Yifan Li Lei Wang Qing-Dao Zeng Yi Liu;Peng Lei;Yang Feng;Shiwei Fu;Xiaoqing Liu;Siqi Zhang;Bin Tu;Chen Chen;Yifan Li;Lei Wang;Qing-Dao Zeng

作者机构：Shenzhen Key Laboratory of Polymer Science and TechnologyGuangdong Research Center for Interfacial Engineering of Functional MaterialsCollege of Materials Science and EngineeringShenzhen UniversityShenzhen 518060China CAS Key Laboratory of Standardization and Measurement for NanotechnologyCAS Center for Excellence in NanoscienceNational Center for Nanoscience andTechnology(NCNST)Beijing100190China Institute of Critical Materials for Integrated CircuitsShenzhen Polytechnic UniversityShenzhen 518055China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2024年第35卷第10期

页      面：233-240页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.21704065,22272039) National Key Basic Research Program of China(No.2016YFA0200700) Guangdong Basic and Applied Basic Research Foundation(No.2023A1515030228) 

主　　题：Conjugated macrocycle Scanning tunneling microscopy Aggregation-induced emission Photochemistry Multicyclicribbon 

摘      要：The topology of conjugated macrocycles had significant impacts on their photo-physical and photochemical ***,a series ofπ-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry *** chemical structure and macrocyclic topology were unambiguously confirmed via NMR,MALDI-TOF mass spectra,crystal analysis and scanning tunneling microscopy(STM).Depending on the structural topology and structural rigidity,these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid *** phenylene vinylene macrocycle(denoted as MST)exhibiting aggregation-induced emission behavior,was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photodimerization due to lower strain and more flourishing intramolecular *** UV light irradiation,relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM *** contrast,highly constrained bicyclic analogue(named as DMTPE)with central tetraphenylethene core,displayed high emission quantum yields of 68%both in solution and in the solid state,and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved[2+2]*** on the solution-mediated photo-polymerization of MST moiety,multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.