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 

机构地区：[1]Shenzhen Key Laboratory of Polymer Science and Technology,Guangdong Research Center for Interfacial Engineering of Functional Materials,College of Materials Science and Engineering,Shenzhen University,Shenzhen 518060,China [2]CAS Key Laboratory of Standardization and Measurement for Nanotechnology,CAS Center for Excellence in Nanoscience,National Center for Nanoscience andTechnology(NCNST),Beijing100190,China [3]Institute of Critical Materials for Integrated Circuits,Shenzhen Polytechnic University,Shenzhen 518055,China

出　　处：《Chinese Chemical Letters》2024年第10期233-240,共8页中国化学快报（英文版）

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)。

摘　　要：The topology of conjugated macrocycles had significant impacts on their photo-physical and photochemical properties.Herein,a series ofπ-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling.Their 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 state.Monocyclic 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 motions.After UV light irradiation,relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation.By 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]photo-dimerization.Based 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.

关 键 词：Conjugated macrocycle Scanning tunneling microscopy Aggregation-induced emission PHOTOCHEMISTRY Multicyclicribbon 

分 类 号：O631.5[理学—高分子化学]