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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (7): 775-782. 上一篇    下一篇

研究论文

二茂铁亚甲基三氮唑配合物的合成、晶体结构及性能研究

周晓莉 李林科 宋瑛林 侯红卫 樊耀亭 孟静静   

  1. 郑州大学化学系
  • 投稿日期:2007-08-10 修回日期:2007-11-22 发布日期:2008-04-14
  • 通讯作者: 侯红卫

Syntheses, Structures and Properties of 1-[(1H-1,2,4-triazol-1-yl)methyl]ferrocene Complexes

  

  • Received:2007-08-10 Revised:2007-11-22 Published:2008-04-14

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641

被引次数

23

以二茂铁亚甲基三氮唑为配体，通过与金属离子的自组装得到了两个新的二茂铁基功能配合物：[Cd(tmf)2(SCN)2]n (1) 和 [Ni(tmf)4(SCN)2] (2) (tmf =二茂铁亚甲基三氮唑)。其中，配合物1呈一维链状结构；配合物2是一个通过氢键作用而形成的二维超分子。三阶非线性光学性质测试结果表明，配合物1（n2 = 2.11 × 10-11 esu）和2（n2 = 1.92 × 10-11 esu）的三阶非线性光学折射效应与配体tmf（n2 = 2.49 ×10-11 esu）接近，说明配合物1和2的三阶非线性光学性质主要受配体控制。循环伏安法(CV)测试结果显示，这两个配合物在电极上的氧化还原过程是受扩散控制的。计时电流法(CA)和计时电量法(CC)测得配合物1的扩散系数比配合物2的扩散系数小。

Two new complexes [Cd(tmf)2(SCN)2]n(1) and [Ni(tmf)4(SCN)2](2) have been synthesized by self-assembly of ligand 1-[(1H-1,2,4-triazol-1-yl)methyl]ferrocene (tmf), SCN- anions and Cd(II) or Ni(II) cations. X-ray crystal diffraction reveals that complex 1 displays one-dimensional double chain structure; complex 2 is a two-dimensional supramolecule formed by hydrogen bonds. The results of the third-order NLO experiments display that the n2 values of complex 1 (2.11 × 10-11 esu) and 2 (1.92 × 10-11 esu) are close to the n2 value of tmf (2.49 ×10-11 esu). This indicates that the third-order NLO properties of complexes 1 and 2 are ruled by tmf ligand. The cyclic voltammetry (CV) studies suggest that the redox processes of complexes 1 and 2 at the electrode are controlled by diffusion. The results of chronoamperometry(CA) and chronocoulometry(CC) show that the values of the diffusion coefficient (D) of complex 1 is smaller than that of complex 2.