一种多孔配位聚合物的氢键协同客体响应  

Guest-responses of A Porous Coordination Polymer Based on Synergistic Hydrogen Bonds

作　　者：莫宗文 张学文 周浩龙 周东东 张杰鹏 MO Zongwen;ZHANG Xuewen;ZHOU Haolong;ZHOU Dongdong;ZHANG Jiepeng(MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China;School of Biotechnology and Health Sciences,Wuyi University,Jiangmen 529000,China)

机构地区：[1]中山大学化学学院,生物无机与合成化学教育部重点实验室,广州510275 [2]五邑大学生物科技与大健康学院,江门529000

出　　处：《高等学校化学学报》2022年第1期82-86,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21731007,21821003,22090061)资助~~。

摘　　要：由硝酸锌、吡唑-3,5-二羧酸(H_(3)pzdc)和2-氨基对苯二甲酸(H_(_(2))abdc)在溶剂热条件下反应得到一种多孔配位聚合物(Me_(2)NH_(2))[Zn_(2)(pzdc)(abdc)]·H_(2)O·DMF(1·g),其中Me_(2)NH_(2)+由溶剂N,N-二甲基甲酰胺(DMF)水解得到,1可视为平行排列的平整带状{Zn_(2)(pzdc)}+链被abdc_(2)−柱子交错支撑而成的三维多孔框架.通过脱附/吸附溶剂分子,中心对称的配位聚合物1·g可以可逆转变成手性的(Me_(2)NH_(2))[Zn_(2)(pzdc)(abdc)](1').单晶结构分析表明,在客体响应过程中,基于框架、抗衡离子和客体分子之间的氢键协作与竞争,抗衡离子发生了显著的移动和转动,导致{Zn_(2)(pzdc)}+链扭曲和转动,伴随着超过10%的晶胞体积和孔洞率变化.气体吸附测试表明,化合物1'对N_(2)和CO_(2)存在不同的结构响应行为.Solvothermal reaction of Zn(NO_(3))_(2)·6H_(2)O,pyrazole-3,5-dicarboxylic acid(H3pzdc)and 2-amino-1,4-benzenedicarboxylic acid(H_(2)abdc)in N,N-dimethylformamide(DMF)produced a porous coordination polymer(Me_(2)NH_(2))[Zn_(2)(pzdc)(abdc)]·H_(2)O·DMF(1·g,g means guest molecules,H_(2)O and DMF),in which Me_(2)NH_(2)+was generated from the hydrolysis of the solvent DMF.The 3-dimensional porous coordination framework of 1 can be re⁃garded as a pillared-ribbon structure consisting of parallelly-aligned flat{Zn_(2)(pzdc)}+ribbons and abdc_(2)−pillars.via desorption/adsorption of solvent molecules,centrosymmetric 1·g can reversibly transform to a chiral framework(Me_(2)NH_(2))[Zn_(2)(pzdc)(abdc)](1').Single-crystal X-ray diffraction analyses showed that,based on the competition and cooperation of hydrogen bonds among the host framework,counter cations,and neutral guest molecules,the counter cations underwent significant movement and rotation in the guest-responsive structural transformations,giving rise to the distortion and rotation of the{Zn_(2)(pzdc)}+ribbon,as well as more than 10%changes of the unit-cell volume and void ratio.Gas adsorption measurements of 1'showed different responses toward N_(2) and CO_(2).

关 键 词：金属有机框架 柔性 客体响应 抗衡离子 

分 类 号：O614.24[理学—无机化学]