Tetraolefin stereospecific photodimerization and photopolymerization in coordination polymers

作     者：Wei-Jie Gong Zhan-Yong Yang Yu-Xuan Hong Dong Liu Zheng Niu Pierre Braunstein Jian-Ping Lang 

作者机构：College of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhou 215123China State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China Jiangsu Key Laboratory for Chemistry of Low-Dimensional MaterialsSchool of Chemistry and Chemical EngineeringHuaiyin Normal UniversityHuaian 223300China Universitéde Strasbourg-CNRSInstitut de Chimie(UMR 7177 CNRS)4 rue Blaise Pascal-CS 90032Strasbourg 67081France 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第10期

页      面：1867-1872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：financially supported by the National Natural Science Foundation of China (NSFC No.21531006,21871196 and 21773163) the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry (No.KF2021005) the Priority Academic Program Development of Jiangsu Higher Education Institutions the Collaborative Innovation Center of Suzhou Nano Science and Technology the Project of Scientific and Technologic Infrastructure of Suzhou(No.SZS201905) the Natural Science Research Program of Jiangsu Provincial Department of Education (No.20KJA150002) Hui-Chun Chin and Tsung-Dao Lee Chinese Undergraduate Research Endowment the Huaishang Talent Program of Huaian 

主　　题：coordination polymers single-crystal to single-crystal transformation photodimerization photopolymerization cycloaddition 

摘      要：In the context of the highly desirable design and preparation of smart materials with adjustable properties based on photoreactive compounds,we report two unique photoreactive coordination polymers(CPs),{[Zn(4-Iba)_(2)(4-tkpvb)]·H_()2O}_(n)(1,4-HIba=4-iodobenzoic acid,4-tkpvb=1,2,4,5-tetrakis(4-pyridylvinyl)benzene)and[Cd(1,4-bdc)(4-tkpvb)]_(n)(2,1,4-H_(2)bdc=1,4-benzenedicarboxylic acid).Depending on the metal ions and auxiliary carboxylate ligands used,the 4-tkpvb ligands in 1 and 2 adopt different mutual arrangements,which facilitate the photodimerization and photopolymerization reactions in single crystal to single crystal(SCSC)*** UV light irradiation which results in the dimerization of the 4-tkpvb ligands,the one-dimensional(1D)zigzag chainsof 1 are transformed into a two-dimensional(2D)network of{[Zn(4-Iba)_(2)(bpbtpvcb)_(0.5)]·H_(2)O}_(n)(1a,bpbtpvcb=1,3-bis(4-pyridyl)-2,4-bis(2,4,5-tri(2-(4-pyridyl)vinyl)phenylcyclobutane).Similarly,in the crystals of 2,all 4-tkpvb ligands experience a photopolymerization reaction to form an unprecedented 1D linear organic polymer,poly-1,3-bis(4-pyridyl)-2,5-bis(2-(4-pyridyl)-vinyl)phenyl)cyclobutane(poly-bpbpvpcb).Furthermore,the 2D network of 2 is converted into a three-dimensional(3D)framework of[Cd_(n)(1,4-bdc)_(n)(poly-bpbpvpcb)](2a).This work not only offers a new protocol to selectively synthesize new supramolecular cyclic compounds,but also expands the application of photopolymerization to the synthesis of macromolecules.