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2025 , Vol. 45 >Issue 4: 1297 - 1305

DOI: https://doi.org/10.6023/cjoc202407022

研究论文

1,3-二叔丁基薁类衍生物的设计合成及性质研究

  • 谢玉龙 ,
  • 向焌钧 ,
  • 宋贤江 ,
  • 张含悦 ,
  • 高希珂
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  • a 中国科学技术大学化学系 合肥 230026
    b 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032
    c 南昌大学国际有序物质科学研究中心 南昌 330031
    d 东南大学生物科学与医学工程学院 数字医学工程全国重点实验室 江苏省生物材料与器件重点实验室 南京 211189

收稿日期: 2024-07-09

  修回日期: 2024-09-27

  网络出版日期: 2024-10-29

基金资助

国家自然科学基金(22225506); 中国科学院战略性先导科技专项(XDB0610000)

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Design, Synthesis, and Properties of 1,3-Di-tert-butylazulene Derivatives

  • Yulong Xie ,
  • Junjun Xiang ,
  • Xianjiang Song ,
  • Hanyue Zhang ,
  • Xike Gao
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  • a Department of Chemistry, University of Science and Technology of China, Hefei 230026
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
    c Ordered Matter Science Research Center, Nanchang University, Nanchang 330031
    d Jiangsu Key Laboratory of Biomaterials and Devices, National Key Laboratory of Digital Medical Engineering, School of Biological Science and Medical Engineering, Southeast University, Nanjing 211189
* E-mail: ;
;

Received date: 2024-07-09

  Revised date: 2024-09-27

  Online published: 2024-10-29

Supported by

National Natural Science Foundation of China(22225506); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)

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摘要

薁是一种为数不多的全碳型偶极分子, 有望通过分子的偶极叠加实现铁电性. 通过理性分析, 设计合成了4个1,3-二叔丁基薁类衍生物, 分别为1,3-二叔丁基薁(1)、1,3-二叔丁基-6-三氟甲基薁(2)、1,3-二叔丁基-6-氟薁(3)和1,3-二叔丁基-5-(6'-薁)基-6-氟薁(4). 这些化合物分别结晶于Aba2、Fdd2、Pna21和Cc空间群, 均属于10个极性点群, 且在晶体中均克服了反平行堆积, 具有宏观极化, 其中化合物4以分子偶极一致的方式堆积, 表明大位阻叔丁基团的引入有效降低了分子间偶极-偶极相互作用. 化合物1和4在300 K时具有明显的二次谐波产生(SHG)信号, 约为典型无机铁电体磷酸二氢钾(KDP)的1/4和2/3. 这些研究结果表明, 在薁单元上进行含氟基团取代和5-位修饰都是使薁类衍生物结晶于10个极性点群的有效策略, 为发展新型薁类有机铁电体提供了研究思路.

关键词： 薁; 分子偶极; 铁电性; 叔丁基; 极性点群

本文引用格式

谢玉龙 , 向焌钧 , 宋贤江 , 张含悦 , 高希珂 . 1,3-二叔丁基薁类衍生物的设计合成及性质研究[J]. 有机化学, 2025 , 45(4) : 1297 -1305 . DOI: 10.6023/cjoc202407022

Abstract

Azulene is one of the few all carbon dipole molecules that is expected to achieve ferroelectricity through the superposition of molecular dipoles. Through rational analysis, four 1,3-di-tert-butylazulene derivatives were synthesized, namely 1,3-di-tert-butylazulene (1), 1,3-di-tert-butyl-6-trifluoromethylazulene (2), 1,3-di-tert-butyl-6-fluoroazulene (3), and 1,3-di-tert-butyl-5-(6'-azulene)-6-fluoroazulene (4). The single crystal structures of these compounds are Aba2, Fdd2, Pna21, and Cc space groups all belong to 10 polar point groups and overcome antiparallel stacking in the crystal, exhibiting macroscopic polarization. Compound 4 is stacked in a molecular dipole consistent manner. This indicates that the introduction of large steric hindrance tert-butyl groups effectively reduces intermolecular dipole-dipole interactions. Compounds 1 and 4 exhibited significant second harmonic generation (SHG) signals at 300 K, which were approximately 1/4 and 2/3 of the typical inorganic ferroelectric potassium dihydrogen phosphate (KDP). These research results indicate that fluoro-group substitution and 5-site modification on azulene units are effective strategies for obtaining azulene derivatives with 10 polar point groups, providing ideas for the development of new azulene organic ferroelectrics.

Key words： azulene; molecular dipole; ferroelectricity; tert-butyl; polar point group

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