高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 861-868.doi: 10.7503/cjcu20170650

• 研究论文: 无机化学 • 上一篇    下一篇

具有穿插结构的金属钴配合物的合成、 结构及电化学性质

赵长江, 刘欣, 田利, 赵仑   

  1. 长春师范大学化学学院, 长春130032
  • 收稿日期:2017-09-26 出版日期:2018-03-29 发布日期:2018-03-29
  • 作者简介:

    联系人简介: 赵 仑, 男, 博士, 教授, 主要从事有机合成及配位聚合物制备方面的研究. E-mail: zhaolun7511@126.com

  • 基金资助:
    吉林省科技厅科技发展计划项目(批准号: 20170101098JC)和长春师范大学研究生教育创新基金项目(批准号: cscxy2017026)资助.

Synthesis, Structure and Electrochemical Properties of Metal Cobalt Complexes with Interpenetrating Structures

ZHAO Changjiang, LIU Xin, TIAN Li, ZHAO Lun*   

  1. College of Chemistry, Changchun Normal University, Changchun 130032, China
  • Received:2017-09-26 Online:2018-03-29 Published:2018-03-29
  • Contact: ZHAO Lun
  • Supported by:
    † Supported by the Science and Technology Development Planning of Jilin Province, China(No.20170101098JC) and the Graduate Education Innovation Fund of Changchun Normal University, China(No.cscxy2017026)

摘要:

在溶剂热体系中合成了3个中心金属为钴离子的具有穿插结构的金属有机配合物{[CoLB]·H2O}n(1), {[Co2L2(bimp)0.5]·3H2O}n(2)和{[Co2L2B'2]·2DMF}n(3) [H2L=4,4'-三苯胺二甲酸; B=1,3-二(咪唑基)苯, bimp=3,5-二(1-咪唑)吡啶, B'=1,4-双(咪唑基)苯]. 通过单晶及粉末X射线衍射和热重分析对这3个配合物进行了表征. 结果表明, 配合物1~3均结晶于单斜晶系, 其中配合物1属C2/c空间群, 配合物2属P2/n空间群, 配合物3属P21空间群; 在配合物1和3中Co2+为四配位模式, 而在配合物2中Co2+为五配位, 并以双核桨轮形的结构单元[Co2(CO2)4]存在; 配合物1和2均为二重穿插结构的三维超分子网络, 配合物3是一个四重穿插的三维超分子网络. 电化学性质研究结果表明, 配合物1~3是电化学活性物质, 电化学可逆性较好.

关键词: 金属有机骨架, 钴配合物, 穿插结构, 循环伏安法

Abstract:

Using multidenate 4,4'-(phenylazanediyl)dibenzoic acid(H2L) and 1,3-bis(imidazol-l-yl)benzene(B), 3,5-bis(imidazol-l-yl)pyridine(bimp) or 1,4-bis(imidazol-l-yl)benzene(B') as ligands under solvothermal conditions, three new metal-organic frameworks with interpenetrating structure, {[CoLB]·H2O}n(1), {[Co2L2(bimp)0.5]·3H2O}n(2) and {[Co2L2B'2]·2DMF}n(3), were synthesized. The complexes were characterized by single-crystal X-ray diffraction(XRD), thermal analysis and powder X-ray diffraction(PXRD). Complexes 1—3 all crystallize in the monoclinic system, with C2/c(complex 1), P2/n(complex 2) and P21(complex 3) space group, respectively. In complexes 1 and 3, Co2+ forms a tetracoordinate geometry, whereas it forms a five-coordinated geometric configuration and exists as a dual-core paddle-shaped structural unit [Co2(CO2)4] in complex 2. Complexes 1 and 2 give a 2-fold interpenetrating three-dimensional(3D) supramolecular networks, while complex 3 exhibits a 4-fold interpenetrating 3D framework. The results of electrochemical studies show that complexes 1—3 are electrochemically active substances with good electrochemical reversibility.

Key words: Metal-organic framework(MOF), Cobalt complex, Interpenetrating structure, Cyclic voltammetry