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

doi:10.6023/cjoc202407022

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (4): 1297-1305.DOI: 10.6023/cjoc202407022 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 发布日期: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)

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

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

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

Received:2024-07-09 Revised:2024-09-27 Published:2024-10-29
Contact: * E-mail: songxj@ncu.edu.cn; zhanghanyue@seu.edu.cn; gaoxk@mail.sioc.ac.cn
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.

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Fig. & Tab. 12

Scheme 1. Synthetic routes of compounds 1~4

Figure 1. 1H NMR spectra of compounds 1~4

Compd.	Temperature/K	Crystal system	Point group	Space group
1	213	Orthorhombic	mm2	Aba2
2	213	Orthorhombic	mm2	Fdd2
3	293	Orthorhombic	mm2	Pna2₁
4	173	Monoclinic	m	Cc

Table 1. Single crystal data of compounds 1~4

Figure 2. Single crystal structure (a) and molecular packing (b) of compound 1

Figure 3. Single crystal structure (a) and molecular packing (b) of compound 2

Figure 4. Single crystal structure (a) and molecular packing (b) of compound 3

Figure 5. Single crystal structure (a) and molecular packing (b) of compound 4

Figure 6. Theoretical calculation of dipole moment for compound 4 (structural optimization and frequency calculation was performed at the B3LYP/6-31G(d,p) theoretical level, and dipole moment calculation was performed at the B3LYP/aug-cc-PVTZ theoretical level)

Compd.	λ_max^a/nm	ε/(L•mol^－1•cm^－1)	λ_edge/nm	$E_{\text{g}}^{\text{opt}}$^b/eV	E_HOMO^c/eV	E_LUMO^d/eV
1	288	1.18×10⁵	808	1.53	－5.17	－3.64
2	290	9.57×10⁴	867	1.43	－5.38	－3.95
3	292	7.24×10⁴	764	1.62	－5.30	－3.68
4	299	1.22×10⁵	756	1.64	－5.20	－3.56

Table 2. Spectral and electrochemical data of compounds 1~4

Figure 7. UV-Vis absorption spectra of compounds 1~4 in dichloromethane solution (the concentration is 1.0×10－5 mol/L)

Figure 8. Cyclic voltammograms of compounds 1~4 in dichloromethane solution With 0.1 mol?L－1 Bu4NPF6 as supporting electrolyte, SCE as reference electrode, scanning rate of 100 mV?s－1. The concentration is 1.0×10－3 mol?L－1

Figure 9. SHG signal intensity of compounds 1~4 and KDP at 300 K

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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-butylazulene Derivatives

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