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Chinese Journal of Organic Chemistry >

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

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

ARTICLES

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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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

Cite this article

Yulong Xie , Junjun Xiang , Xianjiang Song , Hanyue Zhang , Xike Gao . Design, Synthesis, and Properties of 1,3-Di-tert-butylazulene Derivatives[J]. Chinese Journal of Organic Chemistry, 2025 , 45(4) : 1297 -1305 . DOI: 10.6023/cjoc202407022

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