高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (4): 700.

• 研究论文 • 上一篇    下一篇

双-锌卟啉对DABCO分子识别的立体构象及其热力学研究

任奇志1,2, 朱志昂2, 江冬青2, 黄锦汪3, 计亮年3, 陈荣悌2   

  1. 1. 上海交通大学化学化工学院, 上海 200240;
    2. 南开大学化学系, 天津 300071;
    3. 中山大学化学系, 广州 510275
  • 收稿日期:2000-04-12 出版日期:2002-04-24 发布日期:2002-04-24
  • 通讯作者: 朱志昂(1939年出生),男,教授,博士生导师,从事金属卟啉配合物研究.
  • 基金资助:

    国家自然科学基金(批准号:20171024)资助.

Molecular Recognition of Zinc Porphyrin Dimers to DABCO andCorresponding Thermodynamic Study

REN Qi-Zhi1,2, ZHU Zhi-Ang2, JIANG Dong-Qing2, HUANG Jin-Wang3, JI Liang-Nian3, CHEN Yong-Ti2   

  1. 1. School of Chemistry and Chemical Technology, Shanghai Jiaotong University. Shanghai 200240, China;
    2. Department of Chemistry, University, Tianjin 300071, China;
    3. Department of Chemistry, Zhongshan University, Guangzhou 510275, China
  • Received:2000-04-12 Online:2002-04-24 Published:2002-04-24

PDF (PC)

被引次数

16

摘要： 合成了系列不同长度以柔性侧链相连的p/p型双-锌卟啉配合物,用1H NMR和UV-Vis研究了不同温度下该系列配合物与刚性双齿配体DABCO(1,4-二氮杂双环)的轴向配位反应,考察了侧链长度对双-锌卟啉与配体的分子识别能力影响。结果表明,主体分子双-锌卟啉可以对客体分子BABCO进行分子识别,合适长度的柔韧烷氧链可以调节主体分子的构象,使DABCO嵌入双卟啉两个卟啉环间空位中,形成锌卟啉-DABCO-锌卟啉三元夹心式配合物构象。探讨了配位反应中立体构象的变化过程,并测定了热力学参数。

关键词: 双-锌卟啉, 1H NMR, &pi, -&pi, 相互作用, 分子识别, 热力学参数

Abstract: A series of p/p type zinc porphyrin dimers covalently linked with a flexible chain are synthe-sized and characterized.The molecular recognition of zinc porphyrin dimers and corresponding monomer torigid nitrogenous bidentate ligand DABCO (1,4-diazobicyclo[2,2,2]octane) are described in detail by 1H NMR and UV-Vis spectroscopy.DABCOcan bind inside the cavities of porphyrin dimers and form aternary sandwich complex as the length of the alkoxyl chain is long enough and their molar ratio is suit-able.The thermodynamic parameters such as the equilibrium constants, stoichiometric numbers, and thecorresponding enthalpies and entropies of the binding behavior are also obtained by UV-Vis spectroscopy.

Key words: Zinc porphyrin dimer, 1H NMR, π-&pi, interaction, Molecular recognition, Thermodynamic pa-rameter

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