物理化学学报 >> 2011, Vol. 27 >> Issue (06): 1516-1524.doi: 10.3866/PKU.WHXB20110609

光化学和辐射化学 上一篇    下一篇

D-A结构的9,9-二芳基芴类发光材料的合成、表征及性能

欧阳密1, 项文勤1, 张玉建1, 金燕仙2, 张诚1   

  1. 1. 浙江工业大学, 绿色化学合成技术国家重点实验室培育基地, 杭州 310014;
    2. 台州学院医药化工学院, 浙江 临海 317000
  • 收稿日期:2011-01-13 修回日期:2011-03-04 发布日期:2011-05-31
  • 通讯作者: 张诚 E-mail:czhang@zjut.edu.cn
  • 基金资助:

    国家重点基础研究发展计划(973)前期专项(2010CB635108, 2011CB201608), 浙江省自然科学基金(Y4090260)及中国博士后基金(20100471755)资助项目

Synthesis, Characterization and Properties of Electron Donor-Acceptor Complexes Based on 9,9-Diarylfluorene

OUYANG Mi1, XIANG Wen-Qin1, ZHANG Yu-Jian1, JIN Yan-Xian2, ZHANG Cheng1   

  1. 1. State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou, 310014, P. R. China;
    2. School of Chemical Engineering, Taizhou College, Linhai 317000, Zhejiang Province, P. R. China
  • Received:2011-01-13 Revised:2011-03-04 Published:2011-05-31
  • Contact: ZHANG Cheng E-mail:czhang@zjut.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (2010CB635108, 2011CB201608), Natural Science Foundation of Zhejiang Province, China (Y4090260) and National Science Foundation for Post-doctoral Scientists of China (20100471755).

摘要:

设计合成了一系列以三苯胺结构为核心的具有推电子-拉电子(D-A)结构的9,9-二芳基芴类有机小分子. 研究了介质极性对吸收与发射光谱行为的影响及分子结构与其发光能力的关系. 该类化合物荧光发射波长范围在430-530 nm. 并在特定极性溶剂中观察到双重荧光现象. 溶剂效应显示该类化合物随着介质极性的增加, 分子内电荷转移态(ICT)的荧光发射峰波长先红移后蓝移且荧光强度降低, 表现出扭曲的分子内电荷转移(TICT)行为. 该类化合物的最高占有分子轨道(HOMO)能级位于-5.24 - -5.50 eV, 且可以通过改变取代基电负性的强弱来调节. 所得化合物的玻璃化转变温度为192-206 °C, 热重分析(TGA)表明化合物的热分解温度都在400 °C以上, 具有良好的热稳定性.

关键词: 光致发光, 推电子-拉电子结构, 分子内电荷转移, 双荧光, 扭曲的分子内电荷转移

Abstract:

A series of fluorene-triphenylamine derivatives containing an electron donor-acceptor (D-A) structure based on 9,9-diarylfluorene was designed and synthesized. Their optical properties were investigated by UV-Vis spectroscopy and photoluminescence (PL) techniques in solution as well as in the solid state. The maximum PL emission wavelengths of the compounds ranged from 430 to 530 nm. A dual fluorescence phenomenon was observed in particular polar solvents and the relationship between emission properties and molecular structures was studied. The results reveal the existence of a charge transfer (CT) excited state in the molecules and the PL properties of these compounds depend on the structure of the compound and also on the polarity of the solvent. The molecular constitution of the compounds improves the hole-injection issues for fluorene-based materials because of the introduction of a triphenylamine group. Cyclic voltammetry (CV) shows that the highest occupied molecular orbital (HOMO) energy level of the compounds is located between -5.24 and -5.50 eV and it can be tailored by changing the electronegativity of the substituent group. Simultaneously, the spiro-skeleton molecular structure leads to an excellent glass transition temperature (192-206 °C) and it retains good morphological stability. The thermogravimetric (TG) curves of the compounds show a thermal-decomposition temperature of higher than 400 °C.

Key words: Photoluminence, Electron donor-acceptor structure, Intramolecular charge-transfer, Dual fluorescence, Twisted intramolecular charge transfer

MSC2000: 

  • O644