由5-取代基间苯二甲酸和二咪唑衍生物构筑的两个二维钴(II)的配合物的合成、结构及性质
Syntheses, Structures and Properties of 2D Metal-Organic Coordination Polymers Constructed from 5-Substituted Isophthalic Acid and Bis(imidazole) Ligands
作者单位E-mail
杨明星 福建师范大学化学与材料学院, 福州 350007  
刘宇晴 福建师范大学化学与材料学院, 福州 350007  
岑福艳 福建师范大学化学与材料学院, 福州 350007  
陈丽娟 福建师范大学化学与材料学院, 福州 350007  
林深 福建师范大学化学与材料学院, 福州 350007 shenlin@fjnu.edu.cn 
摘要: 通过溶剂热法合成了2个二维钴配位聚合物[Co2(1,4-bib)2(5-hipa)2]n1)(5-H2hipa=5-hydroxyisophthalic acid,1,4-bib=1,4-bis(1-imidazolyl) benzene),[Co(Hbpt)(4,4'-bidpe)]n2)(H3bpt=biphenyl-4,4',5-tricarboxylic acid,4,4'-bidpe=4,4'-bis(imidazol-1-yl) diphenyl ether)。X射线单晶衍射实验测定和结构解析结果表明,配合物12中5-hipa2-、Hbpt2-配体的2个相间羧基将相邻的Co2+连接形成含有Co2O4C2八元环和Co2O4C10十六元环的一维链状结构。一维链之间通过1,4-bib,4,4'-bidpe配体上的咪唑基N原子与相邻Co(Ⅱ)离子配位连结形成二维层状结构。配合物1层与层之间通过相邻层中的5-hipa2-配体的羟基与羧基的分子间氢键连结形成三维超分子网络结构。配合物2中,Hbpt配体的羧基氢与层内的相邻链上参与弱配位羧基氧形成层内氢键。电化学性能测试结果表明,配合物1对氧还原反应具有电催化活性。
关键词: 钴配合物  二维结构  ORR催化剂
基金项目: 国家自然科学基金(No.21571034)和2017年国家级大学生创新创业训练计划项目资助。
Abstract: Two new metal-organic coordination polymers,[Co2(1,4-bib)2(5-hipa)2]n (1) (5-H2hipa=5-hydroxyisophth-alic acid, 1,4-bib=1,4-bis(1-imidazolyl)benzene),[Co(Hbpt)(4,4'-bidpe)]n (2) (H3bpt=biphenyl-3,4',5-tricarboxylic acid, 4,4'-bidpe=4,4'-bis(imidazol-1-yl)diphenyl ether) were obtained under solvothermal conditions and chara-cterized structurally. The meta benzenedicarboxylates in 5-hipa2- and Hbpt2- connect the Co(Ⅱ) ions into 1D carboxylate-cobalt chain structures with 8-membered ring Co2O4C2 and 16-membered Co2O4C10 ring alternately. And the bis(imidazole) ligands further link the adjacent 1D carboxylate-cobalt chains to construct an interesting two-dimensional layered structure, respectively. The adjacent layers[Co2(1,4-bib)2(5-hipa)2] in complex 1 are linked with each other by hydrogen bonding to generate an interesting 3D supramolecular framework. While the hydrogen bonding only exits within the layers of 2. Furthermore, the complex 1/Vulcan XC-72R composite can catalyze the oxygen reduction reaction through a 2e/4e mixed reduction pathway.
Keywords: cobalt (II) complex  2D framework  ORR catalyst
投稿时间:2017-09-28 修订日期:2017-12-05
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杨明星,刘宇晴,岑福艳,陈丽娟,林深.由5-取代基间苯二甲酸和二咪唑衍生物构筑的两个二维钴(II)的配合物的合成、结构及性质[J].无机化学学报,2018,34(3):569-578.
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