物理化学学报 >> 2012, Vol. 28 >> Issue (08): 1992-1999.doi: 10.3866/PKU.WHXB201205282

光化学和辐射化学 上一篇    下一篇

新型三嗪桥连的双1,8-萘酰亚胺衍生物的合成及其光物理行为

申剑磊1, 杨新国1,2, 黄燎1, 沈启立1, 刘振辉1, 张凤菊1   

  1. 1. 湖南大学材料科学与工程学院高分子材料系, 长沙 410082;
    2. 浙江大学硅材料国家重点实验室, 杭州 310027
  • 收稿日期:2012-03-29 修回日期:2012-05-28 发布日期:2012-07-10
  • 通讯作者: 杨新国 E-mail:xgyang@hnu.edu.cn
  • 基金资助:

    国家自然科学基金(50573019), 浙江大学硅材料国家重点实验室开放课题(SKL2009-5)和湖南大学大型精密贵重仪器设备开放基金资助

Synthesis and Photophysical Behavior of Two Novel Bis(1,8-naphthalimides) Containing Triazine Spacers

SHEN Jian-Lei1, YANG Xin-Guo1,2, HUANG Liao1, SHEN Qi-Li1, LIU Zhen-Hui1, ZHANG Feng-Ju1   

  1. 1. Department of Polymer Materials, College of Materials Science & Engineering, Hunan University, Changsha 410082, P. R. China;
    2. State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, P. R. China
  • Received:2012-03-29 Revised:2012-05-28 Published:2012-07-10
  • Contact: YANG Xin-Guo E-mail:xgyang@hnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (50573019), Open Research Program of State Key Laboratory of Silicon Materials, Zhejiang University, China (SKL2009-5), and Open Foundation for Large Precision Instruments of Hunan University.

摘要:

以1,8-萘酰亚胺和三聚氯氰为主要原料, 合成了两种由三嗪环桥连的双1,8-萘酰亚胺化合物3 和5. 采用紫外-可见光谱和荧光光谱等手段考察了两种化合物在不同溶剂中的光物理行为. 与参比化合物N-丁基-1,8-萘酰亚胺相比, 在二氯甲烷、三氯甲烷和甲醇等极性溶剂中, 化合物3和5除了在短波区(λ<400 nm)存在1,8-萘酰亚胺的特征荧光发射峰外, 在长波区(>450 nm)均产生一个较强的新荧光发射峰, 表现出分子内激基缔合物的光物理行为. 与化合物5相比, 由于化合物3特殊的构象异构, 其荧光强度发生严重的猝灭. 在非极性溶剂甲基环己烷中, 化合物5 由于存在较强的分子间氢键作用而聚集, 受激后形成了较稳定的分子间激基缔合物, 但未观察到明显的分子内激基缔合物的形成. 在甲苯溶剂中, 化合物3和5与甲苯分子形成了激基复合物, 并未形成分子内激基缔合物. 进一步研究3和5的固态激发态性质, 发现化合物3和5的固体薄膜受激后分别在465和469 nm处出现激基缔合物的特征荧光发射峰.

关键词: 1,8-萘酰亚胺, 三聚氯氰, 激基缔合物, 激基复合物, 氢键

Abstract:

Two novel bis(1,8-naphthalimides) (3 and 5) containing triazine spacers have been synthesized from 1,8-naphthalic anhydride and cyanuric chloride. The photophysical properties of 3 and 5 have been investigated by UV-Vis absorption and fluorescence spectroscopy. As with N-butyl-1, 8-naphthalimide in polar dichloromethane, chloroform or methanol, the fluorescence spectra of 3 and 5 exhibit a short-wavelength emission band (λ<400 nm) typically observed for 1,8-naphthalimide derivatives, and a broad and red-shifted intramolecular excimer emission band (λ>450 nm). In addition, owing to the specific conformational isomerism, the emission intensity of 3 is significantly quenched by intramolecular electron transfer. In the apolar solvent methyl cyclohexane, the strong hydrogen-bonding interactions between triazine linkers drive monomeric 5 aggregation that is responsible for intermolecular excimer emission. In toluene, both 3 and 5 do not display strong excimer emission. Instead, exciplex formation of toluene with naphthalimide moieties in 3 or 5 is observed. Finally, the excited-state properties of solid films of 3 and 5 have excimer emission around 465 and 469 nm, respectively.

Key words: 1,8-naphthalimide, Cyanuric chloride, Excimer, Exciplex, Hydrogen bond

MSC2000: 

  • O641