高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (7): 1549-1553.doi: 10.7503/cjcu20180116

• 高分子化学 • 上一篇    下一篇

基于四硫富瓦烯和氰基联苯单元的玻璃态液晶化合物的合成及介晶性能

魏福志1,2, 冯微3, 夏艳1,2, 李东风1, 侯瑞斌1,2()   

  1. 1. 长春工业大学化学与生命科学学院,长春 130012
    2. 长春工业大学化学与生命科学学院,长春 130012
    3. 吉林大学中日联谊医院, 长春 130033
  • 收稿日期:2018-02-09 出版日期:2018-07-10 发布日期:2018-06-22
  • 作者简介:联系人简介: 侯瑞斌, 男, 博士, 副教授, 博士生导师, 主要从事功能材料制备方面的研究. E-mail: hrb1018@163.com
  • 基金资助:
    国家自然科学基金(批准号: 21442004)和吉林省教育厅项目(批准号: 2016320)资助.

Synthesis and Mesocrystalline Properties of Glassy Liquid Crystal Compounds Based on Tetrathiofuvalene and Cyanobenzene

WEI Fuzhi1,2, FENG Wei3, XIA Yan1,2, LI Dongfeng1, HOU Ruibin1,2,*()   

  1. 1. College of Chemistry and Life Science Changchun 130012, China
    2. Advanced Institute of Materials Science, Changchun University of Technology, Changchun 130012, China
    3. China-Japan Union Hospital of Jilin University, Changchun 130033, China
  • Received:2018-02-09 Online:2018-07-10 Published:2018-06-22
  • Contact: HOU Ruibin E-mail:hrb1018@163.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21442004) and the Project of Education Department of Jilin Province, China(No.2016320).

摘要:

将性能优良的介晶单元氰基联苯基元引入到四硫富瓦烯(TTF)的外围, 成功合成了3种新型的液晶化合物. 通过核磁共振波谱(NMR)、 傅里叶变换红外光谱(FTIR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)对其结构进行了表征. 利用示差扫描量热分析(DSC)、 热台偏光显微镜(HS-POM)和小角X射线散射(SAXS)实验对3种化合物的液晶相态进行了研究. 结果表明: 合成的3种化合物在宽的温度范围呈现单一液晶相, 在冷却过程中并没有出现结晶现象, 而是转化为玻璃态. 间隔基长度的变化对液晶化合物相态的影响显著, 间隔基较短的化合物呈近晶A相(SmA), 而具有较长间隔基的化合物(1c)呈现六方柱状相. 采用密度泛函(DFT)方法计算了化合物1a的电子结构和前线分子轨道密度分布, 化合物1a的HOMO轨道上的电子云密度集中在TTF上, LUMO集中在氰基联苯上, 说明此类液晶分子为典型的D-σ-A分子.

关键词: 四硫富瓦烯(TTF), 氰基联苯, 玻璃态液晶, 密度泛函理论

Abstract:

Mesocrystalline cyanodiphenyl moiety was introduced to the periphery of tetrathiofuvalene(TTF) to successfully synthesize three new liquid crystal compounds. Their structures were fully characterized by means of NMR, FTIR and MALDI-TOF-MS methods. The liquid crystal phase state of the compounds was studied by differential scanning calorimetry(DSC), hot stage polarizing microscopy(HS-POM) and small angle X-ray scattering(SAXS) experiment. The results demonstrated that the synthesized compounds in the wide range of temperature displayed a single liquid crystal phase and in the cooling process did not appear crystallization phenomenon, but transformed into the glass state. The change of linker length had significant influence on the phase state of liquid crystal compounds. The results illustrated that compound with shorter linker represented smectic A phase(SmA), while compound with longer spacer(1c) presented hexagonal columnar mesophase. The density functional theory(DFT) was used to calculate the electron structure and the electron density distribution of molecular frontier orbital of compound 1a. The results showed that the electron cloud density of the HOMO orbital of compound 1a was concentrated on TTF, and that of LUMO was concentrated on cyanobenzene, indicating that such liquid crystal molecules were typical D-σ-A molecules.

Key words: Tetrathiofuvalene(TTF), Cyanobiphenyl, Glassy liquid crystal, Density functional theory

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