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 

机构地区：[1]College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123,China [2]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China [3]Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials,School of Chemistry and Chemical Engineering,Huaiyin Normal University,Huaian 223300,China [4]Universitéde Strasbourg-CNRS,Institut de Chimie(UMR 7177 CNRS),4 rue Blaise Pascal-CS 90032,Strasbourg 67081,France

出　　处：《Science China Chemistry》2022年第10期1867-1872,共6页中国科学（化学英文版）

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

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)transformations.Upon 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.

关 键 词：coordination polymers single-crystal to single-crystal transformation PHOTODIMERIZATION PHOTOPOLYMERIZATION CYCLOADDITION 

分 类 号：O631.3[理学—高分子化学]