基于三芳胺修饰苯并噻二唑单元偶联的近红外聚集诱导发光分子

doi:10.6023/cjoc202407014

摘要/Abstract

以三芳胺修饰苯并噻二唑作为D-A(给体-受体)单元, 通过钯催化偶联反应合成了3个新型近红外聚集诱导发光分子, 利用核磁共振氢谱及碳谱、高分辨质谱确定了其化学结构. 化合物的二氯甲烷溶液吸收光谱和荧光光谱测试结果显示, 其最大吸收波长分别为525、521和495 nm, 发射峰分别位于791、784和761 nm. 化合物在不同极性溶剂中的光谱测试及理论计算表明其具有分子内电荷转移(ICT)特性. 进一步研究发现所合成化合物在四氢呋喃(THF)/H₂O中具有近红外聚集诱导发光性质, 其发射光谱范围为600~1000 nm, 最高量子产率分别达到了13%、10%和4%. 动态光散射(DLS)和原子力显微镜测试(AFM)结果显示, 所合成化合物在THF/H₂O (V∶V=8∶2)中形成了80 nm左右的球形聚集体.

关键词: 聚集诱导发光(AIE), 近红外发光, 苯并噻二唑, 三芳胺

Three new near-infrared (NIR) aggregation-induced emission (AIE) molecules were constructed by palladium- catalyzed coupling reaction with triarylamine modified benzothiadiazole as a donnor-acceptor (D-A) unit. Their structures were charaterized by ¹H NMR, ¹³C NMR and HRMS. The results of absorption spectroscopic and fluorescence spectroscopic measurements indicated that the absorption maxima of these three compounds in dichloromethean solution were at 525, 521 and 495 nm, respectively, while their emission bands were located at 600~1050 nm. Solvent-dependent spectrosopic studies and theorectical calculations revealed intramolecular charge transfer (ICT) charateristics of these compounds. These compounds exhibited NIR AIE in tetrahydrofuran (THF)/H₂O with emission wavelengths 600~1000 nm and fluorescence quantum yields up to 13%, 10% and 4%, respectively. The results of dynamic light scattering (DLS) and atomic force microscope (AFM) showed that compounds 1~3 formed spherical aggregates of about 80 nm in THF/H₂O (V∶V=8∶2).

Key words: aggregation-induced emission (AIE), near-infrared luminescence, benzothiadiazole, triarylamine

引用此文

董子璇, 苏军军, 潘宏斐, 任相魁, 陈志坚. 基于三芳胺修饰苯并噻二唑单元偶联的近红外聚集诱导发光分子[J]. 有机化学, 2025, 45(1): 205-211.

Zixuan Dong, Junjun Su, Hongfei Pan, Xiangkui Ren, Zhijian Chen. Near-Infrared Aggregation-Induced Emission (AIE) Molecules Based on Coupling of Triarylamine-Modified Benzothiadiazole Units[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 205-211.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图式1. 化合物1~3的合成路线

Scheme 1. Synthetic route of compounds 1~3

图1. 化合物1~3在二氯甲烷溶液中的紫外可见吸收光谱 (c=1.0×10－5 mol/L)

Figure 1. UV-vis absorption spectra of compounds 1~3 in CH2Cl2 (c=1.0×10－5 mol/L)

图2. 化合物1~3的在二氯甲烷溶液中的荧光光谱(c=1.0×10－6 mol/L)

Figure 2. Fluorescence spectra of compounds 1~3 in CH2Cl2 (c=1.0×10－6 mol/L)

Compd.	λ_max/nm	ε^a/(L•mol^－1•cm^－1)	λ_em^b/nm	Stokes shift/nm	Φ ^c/%	τ/ns	E_g^d/eV	HOMO/eV	LUMO/eV
1	525	56200	791	266	2	3.94	1.59	－5.05	－3.46
2	521	42500	784	263	0.1	3.87	1.60	－5.04	－3.44
3	495	35300	761	266	1	1.19	1.64	－5.03	－3.39

表1. 化合物1~3特征数据总结

Table 1. Summary of compounds 1~3 characteristic data

图3. (a)化合物1、(b) 2和(c) 3在不同极性溶剂中的荧光光谱(c=1.0×10－6 mol/L, λex=480 nm, 光谱均做归一化处理)

Figure 3. Fluorescence spectra of compounds (a) 1, (b) 2 and (c) 3 in different polar solvents (c=1.0×10－6 mol/L, λex=480 nm, all spectra were normalized)

图4. HOMO和LUMO轨道示意图

Figure 4. Schematic diagram of the HOMO and LUMO orbitals

图5. (a)化合物1、(b) 2和(c) 3在THF/H2O中的荧光光谱、(d)化合物1~3的荧光强度与含水量的关系[插图: 紫外灯(365 nm)下化合物1~3的THF/H2O溶液(fW=0%, 80%)在比色皿中的照片]及(e)化合物1~3的荧光量子产率与含水量的关系(c=1.0×10－5 mol/L, λex=480 nm)

Figure 5. Fluorescence spectra of compounds (a) 1, (b) 2 and (c) 3 in THF/H2O, (d) the relationship between fluorescence intensity and water content of compounds 1~3 [Insert: photographs of the solution of compounds 1~3 in THF/H2O (fW=0%, 80%) in cuvettes under UV lamp (365 nm)], and (e) the relationship between fluorescence quantum yield and water content of compounds 1~3 (c=1.0×10－5 mol/L, λex=480 nm)

参考文献 30

[1]	Luo, J.; Xie, Z.; Lam, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Commun. 2001, 1740.
[2]	Zhao, Q.; Sun, J. Z. J. Mater. Chem. C 2016, 4, 10588.
[3]	Tu, L.; Xie, Y.; Li, Z.; Tang, B. Z. SmartMat 2021, 2, 326.
[4]	Meng, Q.; Yao, J.; Chen, M.; Dong, Y.; Liu, X.; Zhao, S.; Qiao, R.; Bai, C.; Qu, C.; Miao, H. Anal. Chim. Acta 2023, 1276, 341602.
[5]	Ren, T.; Xu, W.; Zhang, W.; Zhang, X.; Wang, Z.; Xiang, Z.; Yuan, L.; Zhang, X. J. Am. Chem. Soc. 2018, 140, 7716.
[6]	Diao, S.; Blackburn, J. L.; Hong, G.; Antaris, A. L.; Chang, J.; Wu, J. Z.; Zhang, B.; Cheng, K.; Kuo, C. J.; Dai, H. Angew. Chem. 2015, 127, 14971.
[7]	He, Q.; Wang, M.; Zhao, L.; Xu, B.; Tian, W.; Zhang, L. Aggregate 2024, 5, e505.
[8]	Xu, W.; Wang, D.; Tang, B. Angew. Chem., Int. Ed. 2021, 60, 7476.
[9]	Liu, Y.; Phan, H.; Herng, T. S.; Gopalakrishna, T. Y.; Ding, J.; Wu, J. Chem.-Asian J. 2017, 12, 2177.
[10]	Liu, J.; Chen, C.; Ji, S.; Liu, Q.; Ding, D.; Zhao, D.; Liu, B. Chem. Sci. 2017, 8, 2782.
[11]	Lin, J.; Zeng, X.; Xiao, Y.; Tang, L.; Nong, J.; Liu, Y.; Zhou, H.; Ding, B.; Xu, F.; Tong, H.; Deng, Z.; Hong, X. Chem. Sci. 2019, 10, 1219.
[12]	Chen, M.; Zhang, Z.; Lin, R.; Liu, J.; Xie, M.; He, X.; Zheng, C.; Kang, M.; Li, X.; Feng, H.; Lam, J. W. Y.; Wang, D.; Tang, B. Z. Chem. Sci. 2024, 15, 6777.
[13]	Li, T.; Su, C.; Akula, S. B.; Sun, W.; Chien, H. M.; Li, W. Org. Lett. 2016, 18, 3386.
[14]	Pham, H. D.; Wu, Z.; Ono, L. K.; Manzhos, S.; Feron, K.; Motta, N.; Qi, Y.; Sonar, P. Adv. Electron. Mater. 2017, 3, 1700139.
[15]	Feng, Q.; Jia, X.; Zhou, G.; Wang, Z.-S. Chem. Commun. 2013, 49, 7445.
[16]	Peng, Z.; Zhang, K.; Huang, Z.; Wang, Z.; Duttwyler, S.; Wang, Y.; Lu, P. J. Mater. Chem. C 2019, 7, 2430.
[17]	Dang, D.; Zhou, P.; Duan, L.; Bao, X.; Yang, R.; Zhu, W. J. Mater. Chem. A 2016, 4, 8291.
[18]	Xu, Y.; Zhang, H.; Zhang, N.; Wang, X.; Dang, D.; Jing, X.; Xi, D.; Hao, Y.; Tang, B. Z.; Meng, L. ACS Appl. Mater. Interfaces 2020, 12, 6814.
[19]	Abeywickrama. C. S. Chem. Commun. 2022, 58, 9855.
[20]	Sha, J.; Liu, W.; Zheng, X.; Guo, Y.; Li, X.; Ren, H.; Qin, Y.; Wu, J.; Zhang, W.; Lee, C.-S.; Wang, P. Anal. Chem. 2023, 95, 15350.
[21]	Reichardt, C. Chem. Rev. 1994, 94, 2319.
[22]	Zhang, Z.; Edkins, R. M.; Nitsch, J.; Fucke, K.; Eichorn, A.; Steffen, A.; Wang, Y.; Marder, T. B. Chem.-Eur. J. 2015, 21, 177.
[23]	Diurovich, P. I.; Mayo, E. I.; Forrest, S. R.; Thompson, M. E. Org. Electron. 2009, 10, 515.
[24]	Liao, C.; Chen, B.; Xie, Q.; Li, X.; Liu, H.; Wang, S. Adv. Mater. 2023, 35, 2305310.
[25]	Xu, Y.; Zhang, H.; Zhang, N.; Xu, R.; Wang, Z.; Zhou, Y.; Shen, Q.; Dang, D.; Meng, L.; Tang, B. Z. Mater. Chem. Front. 2021, 5, 1872.
[26]	Shen, H.; Sun, F.; Zhu, X.; Zhang, J.; Ou, X.; Zhang, J.; Xu, C.; Sung, H. H. Y.; Williams, I. D.; Chen, S.; Kwok, R. T. K.; Lam, J. W. Y.; Sun, J.; Zhang, F.; Tang, B. Z. J. Am. Chem. Soc. 2022, 144, 15391.
[27]	Wang, C.; Chi, W.; Qiao, Q.; Tan, D.; Xu, Z.; Liu, X. Chem. Soc. Rev. 2021, 50, 12656.
[28]	Hu, R.; Lager, E.; Aguilar-Aguilar, A.; Liu, J.; Lam, J. W. Y.; Sung, H. H. Y.; Williams, I. D.; Zhong, Y.; Wong, K. S.; Peña-Cabrera, E.; Tang, B. Z. J. Phys. Chem. C 2009, 113, 15845.
[29]	Zhuang, Z.; Bu, F.; Luo, W.; Peng, H.; Chen, S.; Hu, R.; Qin, A.; Zhao, Z.; Tang, B. Z. J. Mater. Chem. C 2017, 5, 1836.
[30]	Zhang, J.; Tu, Y.; Shen, H.; Lam, J. W. Y.; Sun, J.; Zhang, H.; Tang, B. Z. Nat. Commun. 2023, 14, 3772.