物理化学学报 >> 2012, Vol. 28 >> Issue (12): 2944-2952.doi: 10.3866/PKU.WHXB201208012

光化学和辐射化学 上一篇    下一篇

基于1,3,5-三嗪的具有力致变色性质的聚集诱导荧光化合物的合成及性质

欧阳密, 俞春辉, 张玉建, 胡彬, 吕晓静, 孙璟玮, 张诚   

  1. 浙江工业大学化学工程与材料学院, 绿色化学合成技术国家重点实验室培育基地, 杭州 310014
  • 收稿日期:2012-06-26 修回日期:2012-07-30 发布日期:2012-11-14
  • 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规划(973)前期专项项目(2010CB635108, 2011CBA00700)及国际科技合作重点项目计划(2012DFA51210)资助

Synthesis and Characterization of New 1,3,5-Triazine-Based Compounds Exhibiting Aggregation-Induced Emission and Mechanochromism

OUYANG Mi, YU Chun-Hui, ZHANG Yu-Jian, HU Bin, Lü Xiao-Jing, SUN Jing-Wei, ZHANG Cheng   

  1. State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou, 310014, P. R. China
  • Received:2012-06-26 Revised:2012-07-30 Published:2012-11-14
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2010CB635108, 2011CBA00700) and International S & T Cooperation Program, China (2012DFA51210).

摘要:

以1,3,5-三嗪为核, 四苯基乙烯为端基, 合成了两种新型的星状结构分子2,4,6-三(4-(1,2,2-三苯基乙烯基)苯基)-1,3,5-三嗪(TTPE-Tr)和2,4,6-三(4-(1,2,2-三苯基乙烯基)-4-联苯基)-1,3,5-三嗪(TTPE-Ph-Tr), 并利用核磁共振(NMR)、离子化质谱(MALDI-MS)及元素分析等对其进行了结构表征. 通过混合溶剂四氢呋喃(THF)/水析出实验显示, 化合物TTPE-Tr和TTPE-Ph-Tr在纯THF溶剂中无荧光, 而在THF/水混合溶剂中, 当水体积分数增加时呈现荧光增强现象. 通过紫外-可见(UV-Vis)光谱、荧光(PL)光谱、扫描电子显微镜(SEM)证实荧光量子效率的提高是由于分子内电子旋转受限(RIR)导致的. 同时发现化合物TTPE-Tr具有力致变色性质, 简单的研磨使其发光颜色(蓝绿光到黄绿光)及发光强度(ΦF, 24.4%到14.7%)发生了明显的改变. UV-Vis光谱、PL光谱、X射线衍射(XRD)、荧光寿命和荧光量子效率等测试结果显示, 这种现象是由于力刺激改变了TTPE-Tr的分子堆积形式导致的. 热分析结果显示化合物TTPE-Tr和TTPE-Ph-Tr的热分解温度分别为464和385℃, 具有良好的热稳定性.

关键词: 1,3,5-三嗪, 四苯基乙烯, 聚集诱导荧光增强, 力致变色, 热稳定性

Abstract:

Two star-shaped molecules consisting of a 1,3,5-triazine core with peripheral tetraphenylethylene moieties, 2,4,6-tris(4-(1,2,2-triphenylvinyl)phenyl)-1,3,5-triazine (TTPE-Tr) and 2,4,6-tris(4-(1,2,2- triphenylvinyl)- [1,1-biphenyl]-4-yl)-1,3,5-triazine (TTPE-Ph-Tr), have been synthesized. These compounds were characterized by nuclear magnetic resonance spectroscopy (NMR), matrix assisted laser desorption/ionization-mass spectrometry (MALDI-MS) and elemental analysis. Both compounds exhibited aggregation-induced emission enhancement (AIEE) properties during addition of water to their tetrahydrofuran (THF) solutions. Results from UV-Vis spectroscopy, photoluminescence (PL) spectroscopy, and scanning electron microscopy (SEM) demonstrated that the restricted intra-molecular bond rotation (RIR) reduced non-radiative transitions in these compounds in the aggregated state, resulting in the fluorescence quantum yields (ΦF) increase. TTPE-Tr was also found to display mechanofluorochromic behavior. This compound, a blue-green powder (ΦF=24.4%, λem=508 nm), exhibited relatively weak yellow/green emission (ΦF=14.7%, λem=517 nm) upon grinding. The phase transition process responsible for this mechanochromism was confirmed by PL spectroscopy, X-ray diffraction (XRD) and time-resolved fluorescence spectroscopy. Thermal analysis of TTPE-Tr and TTPE-Ph-Tr showed that these compounds possess excellent thermal stability, with decomposition temperatures of 464 and 385℃, respectively.

Key words: 1,3,5-Triazine, Tetraphenyl-ethylene, Aggregation-induced emission enhancement, Mechanochromism, Thermal stability

MSC2000: 

  • O644