高等学校化学学报

高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (3): 333.

• 论文 •    下一篇

双卟啉化合物的构象平衡及π-π作用研究

任奇志, 黄锦汪, 林翠梧, 计亮年   

  1. 中山大学化学与化工学院, 广州 510275
  • 收稿日期:1998-07-17 出版日期:1999-03-24 发布日期:1999-03-24
  • 通讯作者: 计亮年
  • 作者简介:任奇志,女,29岁,博士研究生.
  • 基金资助:

    国家自然科学基金;广东省自然科学基金;南京大学配位化学国家重点实验室资助

A Study of Conformation Equilibrium and Interaction of Porphyrin Dimers

REN Qi-Zhi, HUANG Jin-Wang, LIN Cui-Wu, JI Liang-Nian   

  1. School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou, 510275
  • Received:1998-07-17 Online:1999-03-24 Published:1999-03-24

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摘要： 制备并表征了一系列以柔韧烷氧链相连的自由双卟啉及其锌配合物,以1HNMR考察了烷氧链长度及锌离子对双卟啉构象平衡的影响.结果表明,双卟啉存在开放式及闭合式构象平衡,随烷氧链的增长,构象平衡由开放式向闭合式移动,当链上碳原子数为4时最有利于双卟啉形成闭合式构象.锌离子与卟啉环配位后未改变构象平衡趋势.应用IR谱研究了双卟啉环间π-π相互作用,利用荧光光谱考察了双卟啉环间单重态能量转移,其结果支持了1HNMR的结论.

关键词: 双卟啉配合物, 构象平衡, NMR, 化学位移

Abstract: Aseries of porphyrin dimers and their zinc complex covalently linked with _O(CH2)-nO_ chain were synthesized and characterized. Their steady state fluorescence spectra show the existence of intramolecular energy transfer processes in these free base porphyrin dimers. C4free dimer has the greatest efficiency of energy transfer. By using IR and 1HNMR methods, the relationship between the conformation equilibrium and the length of the alkoxyl chain, the metal complexation was studied. With the increase of the length of the chain, the conformation equilibrium of porphyrin dimers moves to the closed conformation, the chain length of C4dimer was suitable to form the closed conformation. The metallation with zinc ion increases the magnitude of π-π interaction of two porphyrin rings while it does not affect the conformation equilibrium of porphyrin dimers.

Key words: Porphyrin dimer, Conformation equilibrium, NMR, Chemical shift

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