应用化学 ›› 2009, Vol. 26 ›› Issue (10): 1216-1221.

• 研究论文 • 上一篇    下一篇

三维超分子配合物[Co2(Dpq)2(btec)(H2O)6]•2H2O的水热合成、晶体结构和电化学性质

林宏艳,王秀丽,刘国成   

  1. (渤海大学化学化工学院 锦州 121000)
  • 收稿日期:2008-09-25 修回日期:2009-02-23 出版日期:2009-10-10 发布日期:2009-10-10
  • 通讯作者: 王秀丽,女,教授; E-mail:wangebw@nenu..edu.cn; 研究方向:配位化学
  • 基金资助:
    辽宁省自然科学基金(20061073)辽宁省教育厅科研基金(2006031)资助项目

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of a 3D Supramolecular Compound: [Co2(Dpq)2(btec)(H2O)6]•2H2O

 LIN Hong-Yan, WANG Xiu-Li, LIU Guo-Cheng   

  1. (College of Chemistry and Chemical Engineering,Bohai University,Jinzhou 121000)
  • Received:2008-09-25 Revised:2009-02-23 Published:2009-10-10 Online:2009-10-10

摘要:

以1,2,4,5-均苯四羧酸(btec)和二-吡啶-(3,2-d:2,3'-f)-二氮萘(Dpq)为混合配体,水热合成了一种三维超分子配合物: [Co2(Dpq)2(btec)(H2O)6]•2H2O (1), 并通过元素分析、红外光谱、热重分析和X-射线衍射法对其结构进行了表征。晶体结构解析结果表明,该配合物属单斜晶系,P21/c 空间群,晶胞参数为:a=0.8978(5)nm, b= 2.9822(16)nm, c= 0.7058(4)nm, β= 94.199(6)º, V= 1.8848(18)nm3, Z= 2, R1= 0.0350, wR2= 0.0796。该化合物由1,2,4,5-均苯四羧酸中羧基氧原子、二-吡啶-(3,2-d:2,3'-f)-二氮萘的螯合氮原子及水分子中氧原子与中心Co(II)离子配位, 形成六配位的扭曲八面体几何构型。羧酸作为桥连配体连接两个相邻的中心Co(II)离子形成钴配合物的双核单元,双核单元之间通过氢键及π-π堆积作用相互连接构成三维超分子网状结构。电化学实验结果表明,钴配合物修饰碳糊电极(1-CPE)在0.1 M 乙酸-乙酸钠缓冲溶液中电位范围+600 – –300 mV内有一对归属于Co(II)/Co(III) 的氧化还原峰,而且此修饰电极对亚硝酸根的氧化有很好的电催化效果。

关键词: 水热合成, 钴配合物, 晶体结构, 超分子网络, 电化学性质

Abstract:

A new 3D Supramolecular compound, [Co2(Dpq)2(btec)(H2O)6]•2H2O (1), has been obtained from hydrothermal reaction of cobalt(II) nitrate with mixed ligands [1,2,4,5-benzenetetracarboxylate (btec) and dipyrido[3,2-d:2′,3′-f]quinoxaline (Dpq)], and structurally characterized by element analysis, IR, TG and single-crystal X-ray diffraction. The result reveals that the compound belongs to monoclinic system with P2(1)/c space group. The cell parameters are: a= 0.8978(5) nm, b= 2.9822(16) nm, c= 0.7058(4) nm, β= 94.199(6) º, V= 1.8848(18) nm3, Z= 2, R1= 0.0350, wR2= 0.0796. The Co(II) is coordinated with two nitrogen atoms of one Dpq molecule, one oxygen atom from bridging ligand btec, and three oxygen atoms belong to coordinated water molecules, respectively, rendering a six-coordinate mode in a distorted octahedron geometry. Each two Co(II) ions are linked by the bridging ligand btec to construct a dinuclear unit . The 3D supramolecular network of title compound is formed through hydrogen bonds and π-π stacking interactions. Moreover, the electrochemical properties of 1 bulk modified carbon paste electrode (1-CPE) have been studied, and the results indicate that the 1-CPE give one-electron redox wave in potential range of 600 to −300 mV due to the metal cobalt ion Co(II)/Co(III). The 1-CPE has good electrocatalytic activity toward the oxidation of nitrite in 0.1 M HAc-NaAc suffer solution.

Key words: hydrothermal synthesis, cobalt compound, crystal structure, supramolecular network, electrochemical property