物理化学学报 >> 2011, Vol. 27 >> Issue (04): 774-780.doi: 10.3866/PKU.WHXB20110432

热力学,动力学和结构化学 上一篇    下一篇

不对称卟啉体系中的弱相互作用

张晓红, 郭洪瑞, 矫志, 闫伟伟, 阮文娟, 朱志昂   

  1. 南开大学化学学院, 天津 300071
  • 收稿日期:2010-12-27 修回日期:2011-02-15 发布日期:2011-03-29
  • 通讯作者: 阮文娟 E-mail:wjruan@nankai.edu.cn
  • 基金资助:

    国家自然科学基金(20671053)资助项目

Weak Interactions in Asymmetric Porphyrin Systems

ZHANG Xiao-Hong, GUO Hong-Rui, JIAO Zhi, YAN Wei-Wei, RUAN Wen-Juan, ZHU Zhi-Ang   

  1. College of Chemistry, Nankai University, Tianjin 300071, P. R. China
  • Received:2010-12-27 Revised:2011-02-15 Published:2011-03-29
  • Contact: RUAN Wen-Juan E-mail:wjruan@nankai.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20671053).

摘要:

采用1H NMR、紫外-可见(UV-Vis)吸收光谱、荧光光谱和分子模拟方法研究了5-邻咪唑甲基苯基-10,15,20-三对叔丁基苯基卟啉(化合物1)和5-对咪唑甲基苯基-10,15,20-三苯基卟啉(化合物2)在氯仿中的弱相互作用. 1H NMR研究表明, 相对于自由咪唑而言, 化合物1和2的侧链咪唑的质子化学位移均向高场移动, 说明两种化合物中存在弱相互作用; 对UV-Vis光谱的研究发现, 与在丙酮中相比, 化合物1在氯仿中的Soret带裂分, 说明在化合物1中存在的是分子内的弱相互作用; 而化合物2的Soret带则发生27 nm的红移, 说明在化合物2中存在的是分子间弱相互作用. 对荧光发射光谱的研究支持上述结论. 对分子的最低能量构象分析得到了与光谱研究一致的结果.

关键词: 弱相互作用, 不对称卟啉, 1H核磁共振, 紫外-可见吸收光谱, 构象分析

Abstract:

The weak interactions of 5-imidazolylmethylphenyl-10,15,20-tri-tert-butylphenylporphyrin (1) and 5-imidazolylmethylphenyl-10,15,20-triphenylporphyrin (2) were investigated in chloroform by 1H NMR, UV-Vis and fluorescence spectroscopies, and molecular modeling simulation. The 1H NMR chemical shifts of imidazole in compounds 1 and 2 move upfield compared with that of free imidazole and this shows that intramolecular or intermolecular weak interactions exist in both compounds. Compared with the UV-Vis spectra of compounds 1 and 2 in acetone, their spectra in chloroform show a split Soret band for compound 1, which indicates a weak intramolecular interaction and a red shift of 27 nm for compound 2, which also suggests a weak intermolecular interaction. The fluorescence data supports these results and the data obtained from the molecular simulation are consistent with those of the spectral analyses.

Key words: Weak interaction, Asymmetric porphyrin, 1H NMR, UV-Vis spectrum, Conformation analysis

MSC2000: 

  • O641