高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (5): 933.

• 研究论文 • 上一篇    下一篇

二茂铁-酞菁-富勒烯超分子三元体系的构筑及光物理和电化学性质

赵海英1,2, 陈晨1, 朱义州1, 郑健禺1   

  1. 1. 南开大学元素有机化学国家重点实验室, 天津 300071;
    2. 内蒙古大学化学化工学院, 呼和浩特 010021
  • 出版日期:2010-05-10 发布日期:2010-05-10
  • 通讯作者: 郑健禺, 男, 博士, 教授, 博士生导师, 主要从事金属有机和超分子化学研究. E-mail: jyzheng@nankai.edu.cn
  • 基金资助:

    国家“九七三”计划项目(批准号: 2006CB932900)、国家自然科学基金(批准号: 20802038, 20721062)和天津市科技计划项目(批准号: 07QTPTJC29700)资助.

Construction, Photophysical and Electrochemical Studies on Ferrocene-phthalocyanine-fullerene Supramolecular Triads

ZHAO Hai-Ying1,2, CHEN Chen1, ZHU Yi-Zhou1, ZHENG Jian-Yu1*   

  1. 1. State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;
    2. College of Chemistry and Chemical Engineering, Inner Mongolia University, Huhhot 010021, China
  • Online:2010-05-10 Published:2010-05-10
  • Contact: ZHENG Jian-Yu. E-mail: jyzheng@nankai.edu.cn
  • Supported by:

    国家“九七三”计划项目(批准号: 2006CB932900)、国家自然科学基金(批准号: 20802038, 20721062)和天津市科技计划项目(批准号: 07QTPTJC29700)资助.

摘要:

采用富勒吡咯烷衍生物中的吡啶或咪唑基与二茂铁修饰的金属酞菁轴向配位构筑了二茂铁-酞菁-富勒烯超分子三元体系, 通过紫外-可见光谱滴定法测定了其配位稳定性(Kassoc约为8.58×104 L/mol). 稳态和时间分辨荧光光谱研究结果表明, 在该超分子三元体系中发生了快速的光诱导电子转移(kCS约为109 s-1), 并具有较高的电荷分离态量子产率(ФCS=0.88). 循环伏安法数据表明, 其电荷分离驱动力ΔGCS为负值(-0.60 eV), 说明酞菁和富勒烯之间容易形成电荷分离态.

关键词: 二茂铁; 酞菁; 富勒烯; 超分子三元体系; 光诱导电子转移

Abstract:

Much attention has been paid recently to the studies on photoinduced electron transfer in donor acceptor systems mainly to develop artificial photosynthetic systems and molecular optoelectronic devices. Several covalent and supramolecular phthalocyanine-fullerene systems have been prepared for this purpose, but only a few triads have been reported to date. In this article, ferrocene-phthalocyanine-fullerene supramolecular triads were constructed with pyridine- or imidazole-appended fulleropyrrolidine and covalently linked zinc phthalocyanine-ferrocene dyad via axial coordination. The stablilities of the triads(Kassoc=8.58×104 L/mol) were studied by optical absorption methods. Steady-state and time-resolved fluorescence measurements suggested that the occurrence of efficient photoinduced electron transfer(kCS =109 s-1) from excited phthalocyanine to fullerene entity in the triads with high charge-separation quantum yields(ФCS =0.88). The redox potentials were determined by cyclic voltammetric, and the driving forces(ΔGCS =-0.60 eV) were estimated to be exothermic, which favored the forming of charge-separation state.

Key words: Ferrocene; Phthalocyanine; Fullerene; Supramolecular triad; Photoinduced electron transfer

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