高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (10): 1509.

• 论文 • 上一篇    下一篇

四-[邻(叔丁氧羰甘氨酸)氨基苯基]卟啉锌配合物的合成、表征及其对咪唑类配体的分子识别

王传忠, 朱志昂, 阮文娟, 李瑛, 严诗楷, 陈荣悌   

  1. 南开大学化学系, 天津 300071
  • 收稿日期:1999-02-26 出版日期:1999-10-24 发布日期:1999-10-24
  • 通讯作者: 朱志昂.
  • 作者简介:王传忠,男,26岁,博士研究生.
  • 基金资助:

    国家自然科学基金(批准号:29871018);元素有机化学国家重点实验室开放基金;南京大学配位化学国家重点实验室资助课题

Synthesis, Characterization and Molecular Recognition of meso-Tetrakis(o-BocGlyamidophenyl)porphyrinatozinc

WANG Chuan-Zhong, ZHU Zhi-Ang, RUAN Wen-Juan, LI Ying, YAN Shi-Kai, CHEN Rong-Ti   

  1. Department of Chemistry, Nankai University, Tianjin 300071, China
  • Received:1999-02-26 Online:1999-10-24 Published:1999-10-24

摘要: 合成并表征了四-[邻(叔丁氧羰甘氨酸)氨基苯基]卟啉H2T(o-BocGly)APP(1)及其锌(Ⅱ)配合物ZnT(o-BocGly)APP(2).用紫外-可见光谱滴定法测定了配合物2与6种咪唑类配体轴向配位反应的平衡常数,研究了它作为主体分子对咪唑类小分子的识别.研究结果表明,各配体的缔合常数按K(Im)>K(2-CH3Im)>K(EMIm)>K(N-CH3Im)>K(2-HOCH2Im)>K(GMZ)的顺序依次减小.计算了卟啉的侧链取代基R与咪唑取代基R′的排斥作用能.测定了轴向配位反应的(这里有图片19991004-1509-1.gif),发现该反应是放热、熵减小的过程,该反应体系中存在焓熵补偿关系.实验发现,R是影响配合物2对咪唑客体识别能力的主要因素.

关键词: 四-[邻(叔丁氧羰甘氨酸)氨基苯基]卟啉锌, 咪唑类配体, 轴向配位反应, 分子识别, 排斥作用能

Abstract: meso-Tetrakis(o-BocGlyamido)porphyrin[H2T(o-BocGly)APP),1] and its zinc complex [ZnT(o-BocGly)APP, 2] were synthesized and characterized. By means of spec-trophotometer technique, the equilibrium constants of the axial coordination reaction were measured between complex 2 and a series of imidazoles, molecular recognition of imidazoles by the receptor porphyrin 2 was studied. The results show that the equilibrium constants de-crease in the orders of K(Im)> K(2-CH3Im)> K(EMIm)> K(2-HOCH2Im) and K (Im)> K(N-CH3Im)> K(GMZ), suggesting that the steric effect was the key factor, the data of steric effect were calculated, the thermodynamic parameters (这里有图片19991004-1514-2.gif) and Δ r S ○? ? m were investigated by van′t Hoff′s equation, the phenomenon of enthalpy-entropy compensation was the observed in the coordination process.

Key words: meso-Tetrakis(o-BocGlyamidophenyl)porphyrinatozinc(Ⅱ), Imidazoles, Axial coordination reaction, Steric repulsion energy, Molecular recognition

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