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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (02): 149-156. 上一篇    下一篇

研究论文

通过铜(II)、铁(III)和铁(II)与2,2'-联咪唑协同作用构筑的超分子及其结构的研究

金琼花*,1，周丽丽1,2，代永成1，徐立军1   

  1. (1首都师范大学化学系 北京 100048)
    (2中国检验检疫科学研究院 北京 100123)
  • 投稿日期:2009-05-24 修回日期:2009-07-19 发布日期:2010-03-17
  • 通讯作者: 金琼花 E-mail:jinqh204@163.com
  • 基金资助:

    国家自然科学基金(No.20871085)资助项目.教育部留学回国人员启动基金.北京市自然科学基金(2092009)北京市教委项目(KM200610028006)和北京市留学人员科技活动择优资助优秀项目.

Crystal Structures of Supramolecular Complexes Built by the Cooperation Effect of Cu(II), Fe(III) and Fe(II) with 2,2-Biimidazole

Jin Qionghua*,1 Zhou Lili1,2 Dai Yongcheng1 Xu Lijun1   

  1. (1 Department of Chemistry, Capital Normal University, Beijing 100048)
    (2 Chinese Academy of Inspection and Quarantine, Beijing 100123)
  • Received:2009-05-24 Revised:2009-07-19 Published:2010-03-17

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在水和乙醇溶剂中, 通过Cu(II), Fe(III)和Fe(II)与2,2-联咪唑协同作用, 构筑了四种新的超分子配合物[Cu(H2biim)(gly)(H2O)]Cl•H2O (1), [Cu(H2biim)(C3H2O4)(H2O)]•1.5H2O (2), [Fe2(μ-O)(H2biim)4(H2O)2](NO3)4•C2H5OH (3)和[Fe(H2biim)3]SO4 (4) (H2biim＝2,2-联咪唑; gly－＝甘氨酸根; C3H2O＝丙二酸根). 并通过元素分析, 红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究. H2biim配体, 丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位. 配合物1～4中, 通过H2biim配体的N—H键与阴离子、水分子和溶剂分子形成多种氢键, 如R(7), R(9)和R(4)等, 以及H2biim配体之间的π-π堆积, 阳离子不对称单元构筑了多维结构的超分子配合物.

关键词: 2,2-联咪唑, 甘氨酸, 丙二酸, 氢键, 铜配合物, 晶体结构

Four new complexes [CuII(H2biim)(gly)(H2O)]Cl•H2O (1), [CuII(H2biim)(C3H2O4)(H2O)]•1.5H2O (2), [FeIII2(μ-O)(H2biim)4(H2O)2](NO3)4•C2H5H (3) and [FeII(H2biim)3]SO4 (4) (H2biim＝2,2'-biimidazole; gly－＝glycinate; C3H2O＝malonate) have been synthesized by the cooperation effect of the metal Cu(II), Fe(III) and Fe(II) with H2biim molecule. 1～4 were characterized by elemental analysis, IR and X-ray single crystal diffraction. In the complexes 1～4, the metal ions are coordinated by chelating biimidazole molecules, glycinate and malonate. By multiple robust hydrogen bonds R(7), R(9) and R(4) formed by N—H groups of biimidazole with anions, water molecules and solvent molecules, complexes 1～4 extend multidimensional structures. 1 and 2 have 3D porous structures, while 3 has a novel binuclear center Fe—O—Fe in which the bridging O atom came from water or air. The Λ-form chiral unit of 4 forms a (10,3) net along b-axis.

Key words: 2,2-biimidazole, glycinate, malonate, hydrogen bond, copper(II) complex, crystal structure