1,3-二叔丁基薁类衍生物的设计合成及性质研究

doi: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^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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摘要/Abstract

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1~4, 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-(6ʹ-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SHG信号, 约为典型无机铁电体KDP(磷酸二氢钾)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

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

引用此文

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, doi: 10.6023/cjoc202407022.

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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