高等学校化学学报

高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (12): 2034.

• 论文 • 上一篇    下一篇

卟啉衍生物π离子自由基二聚体的电子光谱研究

姜月顺1, 杨继华1, 王德军1, 陈咏梅1, 杨文胜1, 白玉白1, 李铁津1, 王永强2   

  1. 1. 吉林大学化学系, 长春 130023;
    2. 北京大学化学系, 北京 100871
  • 收稿日期:1996-11-19 出版日期:1997-12-24 发布日期:1997-12-24
  • 通讯作者: 姜月顺, 女, 55岁, 副教授.
  • 作者简介:姜月顺, 女, 55岁, 副教授.
  • 基金资助:

    国家自然科学基金

Electronic Spectra of π Ion-radical Dimer of Porphyrin Derivatives

JIANG Yue-Shun1, YANG Ji-Hua1, WANG De-Jun1, CHEN Yong-Mei1, YANG Wen-Sheng1, BAI Yu-Bai1, LI Tie-Jin1, WANG Yong-Qiang2   

  1. 1. Department of Chemistry, Jilin University, Changchun 130023;
    2. Department of Chemistry, Peking University, Beijing 100871
  • Received:1996-11-19 Online:1997-12-24 Published:1997-12-24

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摘要： 根据四甲基吡啶铜叶啉(CuTMPyP)的光谱电化学和部分质子化的5,10,15-三(4-羟基苯基)-20－(4-十六烷氧苯基)卟啉(P31)LB膜的荧光光谱,研究了卟琳衍生物离子自由基二聚体的电子光谱．电还原产生的CuTMPyP负离子自由基与基态分子通过SOMO'-LUMO作用形成面对面二聚体,在480nm处出现二聚体的Q带,在820nm处出现π*→π*带．质子化产生的P31正离子自由基与基态分子通过SOMO-HOMO作用形成面对面二聚体,在470～515nm处出现二聚体的Q带吸收,在710nm出现π→π带．与单体Q带相比这些Q带发生蓝移．

关键词: 卟啉衍生物, &pi, 离子自由基, 二聚作用, 光谱电化学, 荧光光谱

Abstract: The electronic spectra of Kion-radical dimer of porphyrin derivatives were studiedbased on the spectroelectrochemistry of copper (Ⅱ)meso-tetrakis (4-N-methylpyridyl) por-phyrin tetrachloride salt(CuTMPyP) and the fluorescence spectra of partly protonized 5, 10,15-(4-hydroxy phenyl)-20-(4-hexadecyloxy phenyl) porphyrin (P31) LB film.The face-to-face dimer formed through the SOMO'-LUMOinteraction between the electroreducedCuTMPyPanion-radical and the ground state molecule shows Qband at 480 nm and π*-π*band at 820 nm.The face-to-face dimer produced by the SOMO-HOMOinteraction betweenthe protonized P31 cation-radical and the ground state molecule shows the Qband absorptionat the range of 470-515 nm; and the π-π band at 710 nm.These Qbands are blue-shifted.

Key words: Porphyrin derivative, &pi, ion-radical, Dimer-interaction, Spectroelectrochemistry, Fluorescence spectrum

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