高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (06): 1205.doi: 10.3969/j.issn.0251-0790.2012.06.015

• 有机化学 • 上一篇    下一篇

磺酰脒基桥连的锌卟啉-富勒烯化合物构型对光诱导电子转移机理的影响

贺林, 陈晨, 李飞, 朱义州, 郑健禺   

  1. 南开大学元素有机化学国家重点实验室, 天津 300071
  • 收稿日期:2011-12-06 出版日期:2012-06-10 发布日期:2012-06-10
  • 通讯作者: 郑健禺, 男, 博士, 教授, 博士生导师, 主要从事金属有机及超分子化学研究. E-mail: jyzheng@nankai.edu.cn E-mail:jyzheng@nankai.edu.cn
  • 基金资助:

    国家"九七三"计划项目(批准号: 2011CB932902)和国家自然科学基金(批准号: 21172126, 20802038)资助.

Influence of Configuration on Photoinduced Electron-transfer Mechanism in Sulfonyl Amidine Linked Porphyrin-fullerene Dyad

HE Lin, CHEN Chen, LI Fei, ZHU Yi-Zhou, ZHENG Jian-Yu   

  1. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
  • Received:2011-12-06 Online:2012-06-10 Published:2012-06-10

摘要: 通过"一锅法"多组分偶联反应合成了一种新型磺酰脒基桥连的卟啉-富勒烯化合物ZnP-H-C60. 该化合物具有Z式和E式2种异构体, 其中Z式异构体中含有分子内氢键. 光物理研究结果表明, 2种异构体中的卟啉与富勒烯之间都可以发生光诱导电子转移, 但其相应的电子转移机理却完全不同. 在Z式异构体中, 卟啉或富勒烯被激发后直接发生电荷分离而形成电荷分离态, 其电荷分离机理是通过氢键进行电子传递; 在E式异构体中, 由于卟啉和富勒烯之间存在空间电子相互作用, 被激发后先形成卟啉-富勒烯激基复合物, 再进一步发生电荷分离形成电荷分离态, 电荷分离通过空间电子转移实现.

关键词: 卟啉, 富勒烯, 光诱导电子转移, 氢键

Abstract: A novel sulfonyl amidine linked porphyrin-fullerene dyad ZnP-H-C60 was facilely synthesized via a three components one-pot coupling reaction. There are two isomers(Z- and E-) in the dyad solution in low-polarity solvents, such as chloroform and toluene. We found that the photoinduced electron-transfer(PET) process could occur in two isomers, but the electron-transfer mechanism was different from each other. The electron transfer process was mediated by the intramolecular hydrogen-bond in (Z-)ZnP-H-C60; and in (E-)ZnP-H-C60, the porphyrin-fullerene exciplex was the precursor of the charge separation(CS) state due to the closer distance between porphyrin and fullerene entities.

Key words: Porphyrin, Fullerene, Photoinduced electron-transfer, Hydrogen-bond

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