化学学报 ›› 2016, Vol. 74 ›› Issue (11): 923-928.DOI: 10.6023/A16080433 上一篇    下一篇

研究论文

高对比度多色力致发光变色二苯并富烯衍生物的设计合成及性质研究

段雨欣, 向雪琴, 董永强   

  1. 能量转换与存储材料北京市重点实验室 北京师范大学化学学院 北京 100875
  • 投稿日期:2016-08-25 发布日期:2016-09-27
  • 通讯作者: 董永强 E-mail:dongyq@bnu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No.51173018)和中央高校基本科研业务费专项资金资助.

Diphenyldibenzofulvene Derivatives Exhibiting Reversible Multicolored Mechanochromic Luminescence with High Contrast

Duan Yuxin, Xiang Xueqin, Dong Yongqiang   

  1. Beijing Key Laboratory of Energy Conversion and Storage Materials, Department of Chemistry, Beijing Normal University, Beijing 100875
  • Received:2016-08-25 Published:2016-09-27
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 51173018) and Fundamental Research Funds for the Central Universities.

制备了苯基甲苯基二苯并富烯(phenyltolyldibenzofulvene,1)并研究了其发光性能.化合物1具有聚集诱导发光(aggregation induced emission,AIE)及结晶诱导荧光增强(crystallization enhanced emission,CEE)的性质,且化合物1可形成蓝色、蓝绿色荧光的晶体以及黄绿色荧光的无定形态.因化合物1分子为扭曲的螺旋桨构象,分子在聚集态中以较疏松的形式堆积,故化合物1可在热、溶剂气氛以及外力刺激下发生多种聚集态间的可逆转变,从而实现在三种不同发光状态间的可逆转变.我们尝试将化合物1用于光学记录,以单一化合物1为发光材料,其可在蓝绿及蓝色荧光颜色背景上以暗黄绿色字迹记录,可通过研磨、加热及溶剂气氛处理擦除字迹,并将记录纸分别转变为蓝色、蓝绿色及黄绿色,因此化合物1有望用于光存储材料.

关键词: 聚集诱导发光, 结晶诱导荧光增强, 螺旋桨构象, 力致发光变色, 光学记录

High performance mechanochromic luminescent (MCL) materials exhibiting multicolored emission switching or high contrast emission color and efficiency have seldom been reported despite their potential application to improve the complexity of anti-fake or increase the density of optical data storage. Through combination of the large conjugation core and peripheral phenyl rings, we designed and synthesized phenyltolyldibenzofulvene (1). Luminogen 1 exhibits aggregation induced emission (AIE) and crystallization enhanced emission (CEE). Luminogen 1 can form blue (1CB, 465 nm, Φ=14.6%) and blue-green (1CA, 485 nm, Φ=13.9%) emissive crystals through slow solvent evaporation of chloroform/hexane and 1,2-dichlorethane/hexane, respectively, and its amorphous solid (1Am, 525 nm, Φ=2.1%) emits dark yellow green light. The propeller-like conformation of 1 affords loose packing pattern and facilitates the morphology tuning in the solid state. Thus, emission of 1 can be switched reversibly among blue, blue-green and yellow-green through modulation of morphology by mechanical stimuli, heating or solvent fuming. Moreover, the mechanochromic luminescence of 1 affords its potential application in optical recording. Ground powder of 1 was dispersed on weighing paper, and a yellow-green emissive paper was obtained. The paper can be transformed to blue and blue-green emissive through solvent fuming, and dark green letters on the blue and blue-green emissive paper could be obtained through writing with glass rod due to the amorphization of luminogen 1 in the written area. The letters can be erased through solvent fuming, heating or grinding, so the paper can be switched to blue, blue-green, or yellow-green emissive depending on the erasing method. Thus, following the strategy of combination of the large conjugation core and peripheral phenyl rings, the obtained luminogen exhibit multicolored MCL emission switching with high contrast. And the molecular design strategy for high performance MCL materials was further verified.

Key words: AIE, crystallization enhanced emission, propeller-like conformation, high performance mechanochromic luminescence, optical recording