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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (13): 1481-1486. 上一篇    下一篇

研究论文

羧脒盐桥介导的萘-二苯酮单重态能量传递研究

韩 镭a,b 李迎迎a 曾 毅a,b 陈金平*,a 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中国科学院研究生院 北京 100039)

  • 投稿日期:2009-04-30 修回日期:2009-05-25 发布日期:2009-07-14
  • 通讯作者: 李嫕

Singlet-Singlet Energy Transfer through an Amidinium-Carboxylate Salt Bridge Interface in Naphthalene-Benzophenone Dyads

Han, Lei a,b Li, Yingying a Zeng, Yi a,b Chen, Jinping *,a 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 Graduate School, Chinese Academy of Sciences, Beijing 100039)
  • Received:2009-04-30 Revised:2009-05-25 Published:2009-07-14
  • Contact: Li, Yi

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设计构建了以羧脒盐桥联接的二苯酮和萘超分子体系, NA-(脒基-羧基)-BP和NA-(羧基-脒基)-BP, 以及相应的模型体系. 稳态和时间分辨荧光光谱研究表明, 置于羧脒盐桥两端的萘和二苯酮基团之间可以发生有效的单重态能量传递, 超分子体系NA-(脒-羧)-BP (NA-Am/BP-COOH＝1/1)和NA-(羧-脒)-BP (NA-COOH/BP-Am＝1/1)中单重态能量传递效率分别为0.998和0.970, 速率常数分别为6.8×1010和1.5×1010 s－1. 推断羧脒盐桥介导了超分子体系中单重态能量传递过程并具备方向性性质, 单重态能量传递“通过键”以电子交换机制进行.

关键词: 羧脒盐桥, 能量传递, 二苯酮, 萘

The amidinium-carboxylate salt bridge systems bearing a pair of energy transfer donor (naphthalene, NA) and acceptor (benzophenone, BP), NA-(amidinium-carboxylate)-BP and NA-(carboxlate- amidinium)-BP, were constructed. Steady state and time-resolved fluorescence studies demonstrate that the singlet-singlet energy transfer from NA to BP can occur efficiently with efficiencies of 0.998, 0.970 and rate constants of 6.8×1010 and 1.5×1010 s―1 for NA-(amidinium-carboxylate)-BP (NA-Am/BP-COOH＝1/1) and NA-(carboxylate-amidinium)-BP (NA-COOH/BP-Am＝1/1), respectively. We infer that the singlet-singlet energy transfer proceeds via a “through-bond” electron exchange mechanism, and the amidinium-car- boxylate salt bridge mediates the energy transfer process with directionality.

Key words: amidinium-carboxylate salt bridge, energy transfer, benzophenone, naphthalene