苯并咪唑类受体(A)-π-供体(D)型小分子蓝紫色传统荧光材料

doi:10.6023/cjoc202501017

摘要/Abstract

通过C—N偶联反应, 分别合成了两种以苯并咪唑类为受体的受体(A)-π-供体(D)型纯有机小分子蓝紫色传统荧光材料, 用¹H NMR、¹³C NMR和HRMS对其分子结构进行确认, 系统地研究了材料的光物理性能、热稳定性和电化学性质, 并对其进行了理论计算. 成功合成了两种CIE_y<0.06的蓝紫色传统荧光材料, 且两者均具有较好的发光性能和热稳定性以及载流子传输特性. 在溶液中均发强蓝紫光, 光学带隙值(E_g)分别为3.17和3.41 eV, 三线态(T₁)能级测试等于2.92和2.81 eV, 绝对荧光量子产率(PLQY)分别为74.33%和81.67%, 平均荧光寿命(τ)高达2.2 ns, 热分解温度最高(T_d)可达436 ℃, 玻璃转化温度(T_g)等于92 ℃, 且均未观察到结晶温度(T_c), 最高占据分子轨道(HOMO)能级分别自为－5.49和－5.71 eV. 这些数据显示, 以这两种材料作为发光材料和主体材料, 通过真空蒸镀法有望获得高效率且长寿命的高性能有机发光二极管(OLED)器件.

关键词: 苯并咪唑, 受体(A)-π-供体(D), 纯有机小分子蓝紫色传统荧光材料, 发光性能, 有机发光二极管(OLED)

Two acceptor (A)-π-donor (D) type pure organic blue purple traditional fluorescent materials with benzimidazole receptors were synthesized through C—N coupling reaction. The molecular structure of the material was confirmed using ¹H NMR, ¹³C NMR, and HRMS. The photophysical properties, thermal stability, and electrochemical properties of the material were systematically studied, and theoretical calculations were performed. The research results show that two traditional blue purple fluorescent materials with CIE_y<0.06 have been successfully synthesized, and both have good luminescence performance, thermal stability, and carrier transport characteristics. Specifically, these compounds emit strong blue purple light in solution with optical bandgap values (E_g) of 3.17 and 3.41 eV, respectively. The triplet states (T₁) energy level test are equal to 2.92 and 2.81 eV, and the absolute fluorescence quantum yields (PLQY) are 74.33% and 81.67%, respectively. The average fluorescence lifetime (τ) is as high as 2.2 ns, and the highest thermal decomposition temperature (T_d) can reach 436 ℃. The glass transition temperature (T_g) is equal to 92 ℃, and no crystallization temperature (T_c) is observed. The highest occupied molecular orbitals. The highest occupied molecular orbital (HOMO) energy levels are －5.49 and －5.71 eV, respectively. These data show that using these two materials as luminescent materials and host materials through vacuum evaporation method is expected to achieve high-performance organic light-emitting diode (OLED) devices with high efficiency and long lifespan.

Key words: benzimidazole, acceptor (A)-π-donor (D), pure organic small molecule blue purple traditional fluorescent material, luminescent properties, organic light-emitting diode (OLED)

引用此文

江小妹, 谭海军, 平力文, 胡振光. 苯并咪唑类受体(A)-π-供体(D)型小分子蓝紫色传统荧光材料[J]. 有机化学, 2025, 45(8): 2896-2906.

Xiaomei Jiang, Haijun Tan, Liwen Ping, Zhenguang Hu. Benzimidazole Acceptor (A)-π-Donor (D) Type Small Molecule Blue Purple Traditional Fluorescent Material[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2896-2906.

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

分享此文

图/表 8

图式1. 目标化合物TBPBI-DPA和TBPBI-Cz的合成路线

Scheme 1. Synthetic routes of target compounds TBPBI-DPA and TBPBI-Cz

图1. (a) TBPBI-DPA和TBPBI-Cz在二氯甲烷中的UV光谱(1.0×10－5 mol/L)以及两者在二氯甲烷中(1.0×10－5 mol/L)和固态下的PL光谱以及(b) TBPBI-DPA和TBPBI-Cz在二氯甲烷中和固态下的CIE色度坐标

Figure 1. (a) UV spectra (1.0×10－5 mol/L) of TBPBI-DPA and TBPBI-Cz in dichloromethane, as well as their PL spectra in dichloromethane (1.0×10－5 mol/L) and in the solid state, and (b) CIE chromaticity coordinates of compounds TBPBI-DPA and TBPBI-Cz in dichloromethane and solid state

图2. (a) TBPBI-DPA和(b) TBPBI-Cz在不同溶剂中的PL光谱(1.0×10－5 mol/L)

Figure 2. PL spectra of (a) TBPBI-DPA and (b) TBPBI-Cz in different solvents (1.0×10－5 mol/L)

图3. TBPBI-DPA和TBPBI-Cz在(a) 2-甲基四氢呋喃中的低温荧光和低温磷光光谱(77 K, 1.0×10－5 mol/L)和(b)二氯甲烷中的室温荧光寿命曲线(1.0×10－5 mol/L)

Figure 3. Fluorescence and phosphorescence spectra of TBPBI-DPA and TBPBI-Cz in (a) 2MeTHF (77 K, 1.0×10－5 mol/L) and DCM at room temperature (1.0×10－5 mol/L)

Compound	Ф_PLQY^a/%	τ^a/ns	K_r^b/s^－1	K_nr^b/s^－1
TBPBI-DPA	74.33	2.20	3.38×10⁸	1.17×10⁸
TBPBI-Cz	81.67	1.52	5.37×10⁸	1.21×10⁸

表1. TBPBI-DPA和TBPBI-Cz的光物理数据

Table 1. Photophysical data of TBPBI-DPA and TBPBI-Cz

图4. TBPBI-DPA和TBPBI-Cz的(a) TGA曲线和(b) DSC曲线

Figure 4. (a) TGA curves and (b) DSC curves of TBPBI-DPA and TBPBI-Cz

图5. TBPBI-DPA和TBPBI-Cz的CV曲线

Figure 5. CV curves of TBPBI-DPA and TBPBI-Cz

图6. TBPBI-DPA和TBPBI-Cz的HOMO和LUMO电子云分布及理论计算的能级

Figure 6. HOMO and LUMO electron cloud distributions and corresponding energy levels of TBPBI-DPA and TBPBI-Cz

参考文献 49

[1]	He, J.; Wu, J.; Wang, J.; Xu, J.; Tang, B. Z.; Zhao, Z. Chin. J. Org. Chem. 2024, 44, 2513 (in Chinese).
	(何俊初, 伍俊琪, 王江辉, 徐静文, 唐本忠, 赵祖金, 有机化学, 2024, 44, 2513.) doi: 10.6023/cjoc202403047
[2]	Miao, J.; Chen, Z.; Xu, P.; Cao, X.; Xu, K.; Zhu, S.; Liu, R.; Li, C.; Song, G. Org. Electron. 2025, 136, 107160.
[3]	Zheng, W.; Zhu, F.; Yan, D. Org. Electron. 2024, 135, 107150.
[4]	Lee, H.; Karthik, D.; Lampande, R.; Ryu, J. H.; Kwon, J. H. Front. Chem. 2020, 8, 373
[5]	Birnstock, J.; Canzler, T.; Hofmann, M.; Lux, A.; Murano, S.; Wellmann, P.; Werner, A. J. Soc. Inf. Disp. 2008, 16, 221.
[6]	Xu, S.; Du, X.; Yang, X.; Hang, H.; Xi, J.; Zhou, G.; Sun, Y. Org. Electron. 2025, 137, 107182.
[7]	Kim, Y. W.; Kim, S.; Lee, C.; Jeong, J. H.; Jeong, Y. H.; Bak, Y.; Kim, S. H.; Park, S. J.; Ham, K. E.; Lee, D.; Song, J.; Song, Y.; Jung, S.-C.; Kwon, O. K.; Han, J.-H.; Kwon, S. J.; Cho, E.-S.; Jeon, Y. Micromachines 2024, 15, 1518.
[8]	Riley, C.; Cho, H.-H.; Brannan, A. C.; Phuoc, N. L.; Linnolahti, M.; Greenham, N. C.; Romanov, A. S. Commun. Chem. 2024, 7, 298.
[9]	Liu, Y.; Ganesan, P.; Chen, M.; Li, Y.; Zhang, Z.; Lin, F.; Zhang, B.; Gao, P. Chem. Eng. J. 2024, 499, 156529.
[10]	Ma, J.-Z.; Li, Y.; Gao, S.; Zhao, Y.; Ding, L.; Zhou, D.-Y.; Fan, J. Acta Chim. Sinica 2025, 83, 17 (in Chinese).
	(马金珠, 李阳, 高珊, 赵越, 丁磊, 周东营, 樊健, 化学学报 2025, 83, 17.) doi: 10.6023/A24100310
[11]	Liu, Z.-Y.; Rao, J.-F.; Zhu, S.-J.; Wang, B.-Y.; Yu, F.; Feng, Q.-Y.; Xie, L.-H. Acta Chim. Sinica 2023, 81, 820 (in Chinese).
	(刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海, 化学学报 2023, 81, 820.) doi: 10.6023/A23040119
[12]	Ge, F.-J.; Zhang, K.-Z.; Cao, Q.-P.; Xu, H.; Zhou, T.; Zhang, W.-H.; Ban, X.-X.; Zhang, X.-B.; Li, N.; Zhu, P. Acta Chim. Sinica 2023, 81, 1157 (in Chinese).
	(葛凤洁, 张开志, 曹清鹏, 徐慧, 周涛, 张文浩, 班鑫鑫, 张晓波, 李娜, 朱鹏, 化学学报 2023, 81, 1157.) doi: 10.6023/A23020051
[13]	Zeng, C.-Y.; Hu, P.; Wang, B.-Q.; Fang, W.-Y.; Zhao, K.-Q.; Donnio, B. Acta Chim. Sinica 2023, 81, 469 (in Chinese).
	(曾崇洋, 胡平, 汪必琴, 方文彦, 赵可清, Bertrand, Donnio, 化学学报 2023, 81, 469.) doi: 10.6023/A23010006
[14]	Ye, Z.-H.; Yang, J.-L.; Ling, Z.-T.; Zhao, Y.; Chen, G; Zheng, Y.-Q.; Wei, B.; Shi, Y. Chin. J. Org. Chem. 2019, 39, 449 (in Chinese).
	(叶中华, 杨佳丽, 凌志天, 赵艺, 陈果, 郑燕琼, 魏斌, 施鹰, 有机化学, 2019, 39, 449.) doi: 10.6023/cjoc201807006
[15]	Zhang, Y.; Nie, F.; Zhou, L.; Wang, X.; Liu, Y.; Huo, Y.; Chen, W.; Zhao, Z. Chin. J. Org. Chem. 2023, 43, 3876 (in Chinese).
	(张越华, 聂飞, 周路, 王晓烽, 刘源, 霍延平, 陈文铖, 赵祖金, 有机化学, 2023, 43, 3876.) doi: 10.6023/cjoc202303022
[16]	Cole, C. M.; Yambem, S. D. Adv. Opt. Mater. 2025, 13, 2402019.
[17]	Zhu, A.; Li, X.; Li, Z.; Si, C.; Miao, Y.; Liu, B.; Yue, G.; Tian, B. Dyes Pigm. 2024, 224, 112017.
[18]	Yang, H. T.; Hyeon, Y. J.; Le, T. N.; Lee, J. E.; Kim, Y.-H.; Suh, M. C. Adv. Opt. Mater. 2024, 12, 2401881.
[19]	Kang, S.; Kim, T. Chem. Phys. Lett. 2024, 856, 141688.
[20]	Lee, C.; Park, S.; Kwon, H.; Lee, K.; Lee, H.; Kang, S.; Park, D.; Park, J. Synth. Met. 2024, 309, 117762.
[21]	Jia, Y.; Wu, S.; Zhang, Y.; Fan, S.; Zhao, X.; Liu, H.; Dong, X.; Wang, S.; Li, X. Org. Electron. 2019, 69, 289. doi: 10.1016/j.orgel.2019.03.044
[22]	Peng, X.-F.; Lei, Y.; Liu, Z.; Ji, X.-X.; Fan, C.-J.; Yang, X.-H. Acta Phys.-Chim. Sin. 2016, 32, 2369.
[23]	Huang, C.; Qiu, Z.-P.; Gao, Y.; Chen, W.-W.; Ji, S.-M.; Huo, Y.-P. Chin. J. Org. Chem. 2021, 41, 3050 (in Chinese).
	(黄酬, 邱志鹏, 高杨, 陈文铖, 籍少敏, 霍延平, 有机化学, 2021, 41, 3050.) doi: 10.6023/cjoc202101053
[24]	Chan, C.-Y.; Tanaka, M.; Lee, Y.-T.; Wong, Y.-W.; Nakanotani, H.; Hatakeyama, T.; Adachi, C. Nat. Photonics 2021, 15, 203.
[25]	Zhao, H.; Han, W.; Bi, Y.; Xu, J.; Ma, X.; Su, C. ChemistrySelect 2024, 9, e202404239.
[26]	Meng, Q.-Y.; Wen, X.-L.; Qiao, J. J. Phys. Chem. Lett. 2024, 15, 12571.
[27]	Li, Z.; Li, Z.; Liu, J.; Han, W.; You, J.; Bin, Z. Chin. J. Org. Chem. 2024, 44, 2006 (in Chinese).
	(李治, 李祯龙, 刘俊杰, 憨卫国, 游劲松, 宾正杨, 有机化学, 2024, 44, 2006.) doi: 10.6023/cjoc202312006
[28]	Tselekidou, D.; Papadopoulos, K.; Andrikopoulos, K. C.; Andreopoulou, A. K.; Kallitsis, J. K.; Logothetidis, S.; Laskarakis, A.; Gioti, M. Nanomaterials 2024, 14, 1623.
[29]	Xu, H.; Yan, H.; Chen, J.; Zhang, X.; Zhang, P.; Li, H.; Meng, H. ACS Appl. Mater. Interfaces 2024, 16, 54574.
[30]	Zhu, B.; Sun, T.; Guo, S.; Zhou, H.; Shi, W.; Huang, J.; Wei, B.; Miao, Y.; Wang, H. Dyes Pigm. 2023, 215, 111251.
[31]	Dong, W.; Bai, Y.; Wang, Y.; Zhao, S.; Xu, H.; Miao, Y.; Luo, Q.; Wang, H.; Yu, J. Sci. China Mater. 2024, 67, 197.
[32]	Shi, Y.; Shi, H.; Wang, H.; Chen, C.-J.; Li, Y.; Qiao, B.; Liang, Z.; Zhao, S.; Hang, D.; Xu, Z.; Song, D. Chem. Eng. J. 2024, 500, 157082.
[33]	Xie, M.; Zhou, Y.; Zhang, L.; Song, J.; Ma, C.; Sun, Q.; Zhang, S.-T.; Yang, W.; Xue, S. Chem. Eng. J. 2024, 500, 156905.
[34]	Li, G.; Xu, K.; Zheng, J.; Fang, X.; Lou, W.; Zhan, F.; Deng, C.; Yang, Y.-F.; Zhang, Q.; She, Y. J. Am. Chem. Soc. 2024, 146, 1667.
[35]	Khotele, N.; Kalyani, N. T.; Pode, R.; Dhoble, S. J. ECS J. Solid State Sci. Technol. 2021, 10, 076006.
[36]	Lu, T.; Huo, Y.; Fang, X.; Ouyang, X. Chin. J. Org. Chem. 2013, 33, 2063 (in Chinese).
	(陆天华, 霍延平, 方小明, 欧阳新华, 有机化学, 2013, 33, 2063.) doi: 10.6023/cjoc201301078
[37]	Wang, Y.-F.; Li, M.; Chen, C.-F. Acta Chim. Sinica 2023, 81, 588 (in Chinese).
	(王银凤, 李猛, 陈传峰, 化学学报 2023, 81, 588.) doi: 10.6023/A23040153
[38]	Liu, Y.; Chen, J.; Shao, Z.; Wei, Y.; Ling, H.; Xie, L. Acta Chim. Sinica 2023, 81, 1508 (in Chinese).
	(刘玉玉, 陈捷锋, 邵振, 魏颖, 凌海峰, 解令海, 化学学报 2023, 81, 1508.) doi: 10.6023/A23060267
[39]	Yin, X.; Wu, Z.-X.; Pang, E.-B; Zhu, Y.-J.; Wang, H.-Z; Zhu, W.-Q.; He, Y. Acta Polym. Sin. 2021, 52, 1578.
[40]	Serevicius, T.; Nakagawa, T.; Kuo, M.-C.; Cheng, S.-H.; Wong, K.-T.; Chang, C.-H.; Kwong, R. C.; Xia, S.; Adachi, C. Phys. Chem. Chem. Phys. 2013, 15, 15850.
[41]	Lee, D. R.; Kim, M.; Jeon, S. K.; Hwang, S.-H.; Lee, C. W.; Lee, J. Y. Adv. Mater. 2015, 27, 5861.
[42]	Lin, D.; Song, S.; Chen, Z.; Guo, P.; Chen, J.; Shi, H.; Mai, Y.; Song, H. Chin. J. Org. Chem. 2018, 38, 103 (in Chinese).
	(林丹燕, 宋森川, 陈智勇, 郭鹏然, 陈江韩, 史华红, 麦裕良, 宋化灿, 有机化学, 2018, 38, 103.) doi: 10.6023/cjoc201709047
[43]	Guo, Y.; Li, Y.; Zhao, Y.; Han, M.; Zhang, D.; Su, W.; Yu, T. Dyes Pigm. 2024, 231, 112417.
[44]	Kim, Y. M.; Yu, S. J. Am. Chem. Soc. 2003, 125, 1696.
[45]	Shavaleev, N. M.; Eliseeva, S. V.; Scopelliti, R.; Bunzli, J.-C. G. Inorg. Chem. 2010, 49, 3927. doi: 10.1021/ic100129r pmid: 20302272
[46]	Semeniuchenko, V.; Braje, W. M.; Organ, M. G. Chem.-Eur. J. 2021, 27, 12535.
[47]	He, W.-Z. M.S Thesis, Liaoning University of Science and Technology, Anshan, 2020 (in Chinese).
	(何文泽, 硕士论文, 辽宁科技大学, 鞍山, 2020.)
[48]	Zhang, R.; Sun, H.; Zhao, Y.; Tang, X.; Ni, Z. Dyes Pigm. 2018, 152, 1.
[49]	Wang, T. M.S Thesis, Peking University, Beijing, 2021 (in Chinese).
	(王涛, 硕士论文, 北京大学, 北京, 2021.)