高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2421.doi: 10.7503/cjcu20150445

• 有机化学 • 上一篇    下一篇

类杯芳烃孔穴桥联双芘分子开关化合物

徐海(), 赵斯祺, 任扬, 蔡健峰, 汪翔, 林雨霖   

  1. 中南大学化学化工学院, 长沙 410083
  • 收稿日期:2015-06-08 出版日期:2015-12-10 发布日期:2015-10-10
  • 作者简介:联系人简介: 徐 海, 男, 博士, 副教授, 主要从事分子开关、 卟啉环和富勒烯方面的研究. E-mail:xhisaac@csu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21002127, 212501100517)资助

Bridged Di-py-cavitand Compounds as Molecular Switch

XU Hai*(), ZHAO Siqi, REN Yang, CAI Jianfeng, WANG Xiang, LIN Yulin   

  1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
  • Received:2015-06-08 Online:2015-12-10 Published:2015-10-10
  • Contact: XU Hai E-mail:xhisaac@csu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21002127, 212501100517)

摘要:

利用构型可变的分子开关类杯芳烃孔穴化合物(Cavitand)作为母体, 合成了2种具有不同臂长的双芘Cavitand化合物. 在室温及中性状态下, 2种双芘Cavitand化合物均可检验出分子内激基复合物荧光, 其中短臂双芘Cavitand化合物的荧光明显强于长臂Cavitand化合物. 经三氟乙酸酸化后, 2种双芘化合物的分子内激基复合物荧光消失; 而继续使用碱中和至中性, 则荧光恢复. 这个荧光出现-消失-出现的过程验证了Cavitand母体化合物分子构型闭合-打开-闭合可有效调控分子激基复合物荧光开关过程. 此外, 通过高斯计算模拟了2种化合物的理论分子构型, 发现长臂双芘化合物在Cavitand母体构型处于闭合状态时2个芘基团重叠部分较少是其分子内激基复合物荧光较弱的关键原因.

关键词: 分子开关, 类杯芳烃孔穴化合物, 荧光, 双芘Cavitand化合物

Abstract:

Two kinds of di-py-cavitand compounds with different arm lengths were synthesized using molecular switch which configurations are variable-class calixarene cavities(Cavitand) as the parent compounds. In the neutral state of room temperature, the two kinds of di-py-cavitand compounds can detect intramolecular exciplex fluorescence and the compounds with short arm is obviously more stronger than the long arm one in the fluorescence intensity. However, intramolecular exciplex fluorescence disappears after acidification by trifluoroacetic acid and appears again when continuing to add alkali so as to neutralize to neutral state. The process of fluorescence appearing-disappearing-appearing powerfully verified that the process of closing-opening-closing of the molecular configuration of cavitand parent compounds can efficiently control intramolecular exciplex fluorescence’s opening and closing processes. In addition, the molecular configurations of di-py-cavitand compounds in theory with different arm length were simulated through Gaussian calculation module, finding that two pyrene groups of di-py-cavitand compound with long arm were less overlaped when the cavitand parent configuration was in the closing state, which is the key cause of the corresponding weak intramolecular exciplex fluorescence intensity.

Key words: Molecular switch, Class calixarene cavities compounds(Cavitand), Fluorescence, Di-py-cavitand compound

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