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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (18): 2023-2029. 上一篇    下一篇

研究论文

Hamilton受体与萘之间光诱导电子转移和三重态能量传递研究

赵 鑫a,c 李迎迎a 李沙渝b 曾 毅a,c
陈金平*,a 杨国强b 李 嫕*,a

  

  1. (a光化学转换与功能材料重点实验室 中国科学院理化技术研究所 北京 100190)
    (b北京分子科学国家实验室 光化学重点实验室 中国科学院化学研究所 北京 100190)
    (c中国科学院研究生院 北京 100039)

  • 投稿日期:2008-02-04 修回日期:2008-04-11 发布日期:2008-09-28
  • 通讯作者: 李嫕

Photoinduced Electron Transfer and Triplet Energy Transfer in Hamilton Receptor-Naphthalene Dyads

ZHAO, Xin a,c LI, Ying-Ying a LI, Sha-Yu b ZENG, Yi a,c
CHEN, Jin-Ping *,a YANG, Guo-Qiang b LI, Yi *,a
  

  1. (a Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190)
    (b Beijing National Laboratory for Molecular Sciences ＆ Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190)
    (c Graduate School, Chinese Academy of Sciences, Beijing 100039)
  • Received:2008-02-04 Revised:2008-04-11 Published:2008-09-28
  • Contact: LI, Yi

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将两个2,6-二氨基吡啶衍生物与异酞酸相连, 得到一个袋状巴比妥酸衍生物受体(Hamilton受体, H-receptor), 同时合成了带有萘基团的巴比妥酸衍生物(G-Np), 两者在非极性溶剂中形成氢键体系, 二氯甲烷溶剂中表观结合常数KAPP＝(4.9±0.5)×104 mol－1•L. 稳态荧光发射光谱和磷光发射光谱研究表明, 室温下H-receptor和G-Np之间主要发生单重态电子转移过程, 77 K下, H-receptor与G-Np之间发生三重态能量传递过程. 本研究为Hamilton氢键体系的理论研究提供了一个新的模型, 对理解氢键在生命体系中的作用有重要的意义.

关键词: 氢键, Hamilton受体, 光致电子转移, 三重态能量传递

A naphthalene-barbiturate conjugant (G-Np) and a pockety barbiturate receptor (Hamilton receptor, H-receptor) with two 2,6-diaminopyridine groups linked through an isophthalic acid spacer were synthesized. The dyad is created by functionalizing the H-receptor and G-Np with six hydrogen bonds, which provide a high apparent association constant (KAPP approximately equal to (4.9±0.5)×104 mol－1•L in CH2Cl2). Excitation with 330 nm light mainly results in a singlet electron transfer between naphthalene and the H-receptor at room temperature, and a triplet energy transfer from the H-receptor to naphthalene at 77 K. These findings provide a new model for the study of the Hamilton hydrogen-bonded system, and will benefit understanding the role of hydrogen bonding in natural assemblies.

Key words: hydrogen bond, Hamilton receptor, photoinduced electron transfer, triplet energy transfer