Design, Synthesis, and Properties of 1,3-di-tert-butyl Azulene Derivatives

doi:10.6023/cjoc202407022

Chinese Journal of Organic Chemistry Previous Articles Next Articles

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1,3-二叔丁基薁类衍生物的设计合成及性质研究

谢玉龙^a,b, 向焌钧^b, 宋贤江^c,*, 张含悦^d,*, 高希珂^b,*

^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江苏省生物材料与器件重点实验室数字医学工程全国重点实验室南京 211189

收稿日期:2024-07-09 修回日期:2024-09-27
基金资助:
国家自然科学基金(No. 22225506)、中国科学院战略性先导科技专项 B 类(Grant No. XDB0610000).

Design, Synthesis, and Properties of 1,3-di-tert-butyl Azulene Derivatives

Xie Yulong^a,b, Xiang Junjun^b, Song Xianjiang^c,*, Zhang Hanyue^d,*, Gao Xike^b,*

^aDepartment of Chemistry, University of Science and Technology of China, Hefei 230026;
^bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
^cOrdered Matter Science Research Center, Nanchang University, Nanchang 330031;
^dSchool of Biological Science and Medical Engineering, Southeast University, Jiangsu Key Laboratory of Biomaterials and Devices, National Key Laboratory of Digital Medical Engineering, Nanjing 211189

Received:2024-07-09 Revised:2024-09-27
Contact: * E-mail: songxj@ncu.edu.cn, zhanghanyue@seu.edu.cn, gaoxk@mail.sioc.ac.cn
Supported by:
National Natural Science Foundation of China (No. 22225506), the Strategic Priority Research Program of the Chinese Academy of

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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-butyl azulene derivatives 1~4 were synthesized, namely 1,3-di-tert-butyl azulene 1, 1,3-di-tert-butyl-6-trifluoromethylazulene 2, 1,3-di-tert-butyl-6-fluoroazulene 3, and 1,3-di-tert-butyl-5-(6ʹ-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 exhibit significant SHG signals at 300 K, which are approximately 1/4 and 2/3 of the typical inorganic ferroelectric KDP (potassium dihydrogen phosphate). 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, ferroelectricity, molecular dipole, tert-butyl, polar point groups

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Xie Yulong, Xiang Junjun, Song Xianjiang, Zhang Hanyue, Gao Xike. Design, Synthesis, and Properties of 1,3-di-tert-butyl Azulene Derivatives[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202407022.

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1,3-二叔丁基薁类衍生物的设计合成及性质研究

Design, Synthesis, and Properties of 1,3-di-tert-butyl Azulene Derivatives

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