基于四氢喹啉的多重共振热活化延迟荧光材料的设计、合成及电致发光性能研究

doi:10.6023/cjoc202301021

摘要/Abstract

多重共振型热活化延迟荧光(MR-TADF)材料是实现超高清有机电激光显示(OLED)的热门材料. 以经典的5,9-二苯基-5,9-二氢-5,9-二氮杂-13b-硼化萘并[3,2,1-de]蒽(DABNA-1)为核心结构, 设计并合成了两种基于四氢喹啉的有机硼类MR-TADF分子5,9-双(1,2,3,4-四氢喹啉)-5,9-二氢-5,9-二氮杂-13b-硼化萘并[3,2,1-de]蒽(THQBN)和7-(叔丁基)-5,9-双(6-(叔丁基)-4,4-二甲基-1,2,3,4-四氢喹啉)-5,9-二氢-5,9-二氮杂-13b-硼化萘并[3,2,1-de]蒽(Tt-THQBN), 使用核磁和质谱对其结构进行表征, 且对两个分子的热稳定性、电化学性质和光物理性质进行了测试. 与经典的MR-TADF材料相同, 这两种分子具有深蓝发光颜色、较窄的半峰宽以及较高的光致发光量子产率. 以THQBN和Tt-THQBN作为客体材料制备的电致发光器件均具有在455~458 nm处的深蓝色发光, 器件2~4的CIE-y都小于0.1, 且半峰宽较窄, 在34~38 nm范围内. 它们的最大亮度可超过1000 cd•m^–2, 并且在该亮度下未发生严重的效率滚降, 其中性能表现较好的器件3在1000 cd•m^–2的初始亮度下器件寿命LT₉₀可达到99 h.

关键词: 多重共振型热活化延迟荧光, 有机硼化合物, 半峰宽, 器件寿命

Multiresonant thermally activated delayed fluorescence (MR-TADF) materials are a series of hot materials to realize ultra-high definition organic light-emitting diode (OLED) display. 5,9-Bis(1,2,3,4-tetrahydroquinoline)-5,9-dihydro-5,9- diaza-13b-boranaphtho[3,2,1-de]anthracene (THQBN) and 7-(tert-butyl)-5,9-bis(6-(tert-butyl)-4,4-dimethyl-1,2,3,4-tetra- hydroquinoline)-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (Tt-THQBN) were designed and synthesized as organoboron based MR-TADF based on tetrahydroquinoline, whose structures were characterized by nuclear magnetic resonance and mass spectrum. The thermal stabilities, electrochemical properties and photophysical properties of these two molecules were measured. They had the similar deep-blue photoluminescence, narrow full-width at half-maximum and high photoluminescence quantum yield with the classical MR-TADF molecules. OLED devices were fabricated employing THQBN and Tt-THQBN as the guest materials. They all had deep blue emission at 455~458 nm. The CIE-y values of devices 2~4 are less than 0.1, and the full width of half maximum (FWHMs) of all devices were narrow, whitin the range of 34~38 nm. Their maximum brightness can exceed 1000 cd•m^–2 without serious efficiency roll-down. The device lifetime LT₉₀ of device 3 with best performance in these devices can reach 99 h at the initial brightness of 1000 cd•m^–2.

Key words: multiresonant thermally activated delayed fluorescence, organoboron based compound, full-width at half- maximum, device lifetime

引用此文

梁凯淳, 白科研, 戴雷, 刘源, 叶泽聪, 霍延平. 基于四氢喹啉的多重共振热活化延迟荧光材料的设计、合成及电致发光性能研究[J]. 有机化学, 2023, 43(5): 1799-1807.

Kaichun Liang, Keyan Bai, Lei Dai, Yuan Liu, Zecong Ye, Yanping Huo. Design, Synthesis and Electroluminescent Properties of Multiresonant Thermally Activated Delayed Fluorescence Materials Based on Tetrahydroquinoline[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1799-1807.

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图/表 10

图式1. 目标化合物的合成路线

Scheme 1. Synthetic route of target compounds

图1. THQBN和Tt-THQBN的TGA (a)、DSC (b)和氧化(c)曲线

Figure 1. Curves of TGA (a), DSC (b) and oxidation (c) of THQBN and Tt-THQBN

Compd.	λ_abs^a/nm	λ_em^a/nm	FWHM/nm	PLQY^b/%	τ_p/ns	τ_d/μs	T_d^c/℃	T_m/℃	HOMO/eV	LUMO/eV	E_g/eV	ΔE_ST^d/eV
THQBN	435	449	24.5	83.4	6.1	51.1	356	201	–5.08	–2.34	2.74	0.09
Tt-THQBN	436	449.5	27.1	85.7	5.8	63.6	381	200	–4.99	–2.27	2.72	0.15
t-DABNA	445	459	22.3	82.9	—	—	419	—	–5.72	–3.02	2.70	0.09

表1. THQBN和Tt-THQBN的光物理和电化学性质

Table 1. Photophysical and electrochemical data of THQBN and Tt-THQBN

图2. THQBN、Tt-THQBN和t-DABNA的紫外-可见吸收谱图和室温发射光谱图

Figure 2. UV-Vis absorption spectra and PL spectra at room temperature of THQBN, Tt-THQBN and t-DABNA

图3. 77 K时THQBN和Tt-THQBN的磷光光谱图以及荧光光谱图

Figure 3. Phosphorescence and fluorescence spectra of THQBN and Tt-THQBN at 77 K

Compd.	Ф^a	Ф_F^b	Ф_TADF^b	k_F^c×10⁸/s^–1	k_IC^c×10⁷/s^–1	k_ISC^c×10⁶/s^–1	k_RISC^c×10⁴/s^–1	k_nr^d×10⁷/s^–1	ΔE_ST^c/eV
THQBN	0.834	0.814	0.020	1.33	2.66	3.94	1.68	3.17	0.19
Tt-THQBN	0.857	0.819	0.038	1.41	2.36	7.63	1.42	2.88	0.20

表2. THQBN和Tt-THQBN的光物理数据

Table 2. Photophysical data of THQBN and Tt-THQBN

图4. THQBN和Tt-THQBN的前线分子轨道计算

Figure 4. Theoretic calculation of frontier molecular orbitals of THQBN and Tt-THQBN

图5. 器件的能级图(a)及器件中所用材料的化学结构(b)

Figure 5. Energy level diagram of the device (a) and chemical structure of materials used in the device (b)

Device	EL(λ_max)/nm	FWHM/nm	V_on/V	CE_max^a/CE₁₀₀₀^b/(cd•A^–1)	LT₉₀^c/h
1	456	37	3.2	4.3/4.2	78
2	455	34	3.2	4.0/3.9	90
3	457	37	3.2	4.5/4.2	99
4	458	38	3.2	4.5/4.3	87

表3. 器件1~4的电致发光数据

Table 3. Electroluminescent data of device 1~4

图6. Devices 1~4的电致发光光谱图(a)、电流密度-电压-亮度(J-V-L)曲线(b)、电流效率-亮度-功率效率(CE-L-PE)曲线(c)及器件百分比亮度衰减至90%曲线(d)

Figure 6. Electroluminescence spectra (a), current density-voltage-luminance (J-V-L) curves (b), current efficiency-luminance-power efficiency (CE-L-PE) curves (c) and lifetime (LT90) curve (d) of devices 1~4

参考文献 42

[1]	Tang, C. W.; Vanslyke, S. A. Appl. Phys. Lett. 1987, 51, 913. doi: 10.1063/1.98799
[2]	Nie, F.; Huang, G. B.; Dai, L.; Chen, S. F.; Ji, S. M.; Chen, J. X.; Huo, Y. P. Chin. J. Org. Chem. 2019, 39, 1423. (in Chinese)
	(聂飞, 黄观波, 戴雷, 陈少福, 籍少敏, 陈嘉雄, 霍延平, 有机化学, 2022, 42, 1423.) doi: 10.6023/cjoc202112039
[3]	Kim, J. U.; Park, I. S.; Chan, C. Y.; Tanaka, M.; Tsuchiya, Y.; Nakanotani, H.; Adachi, C. Nat. Commun. 2020, 11, 1765. doi: 10.1038/s41467-020-15558-5
[4]	Hatakeyama, T.; Ikuta, T.; Shiren, K.; Nakajima, K.; Ni, J. Adv. Mater. 2016, 28, 2777. doi: 10.1002/adma.201505491
[5]	Suresh, S. M.; Hall, D.; Beljonne, D.; Olivier, Y.; Zysman-Colman, E. Adv. Funct. Mater. 2020, 30, 1908677. doi: 10.1002/adfm.v30.33
[6]	Han, S. H.; Jeong, J. H.; Yoo, J. W.; Lee, J. Y. J. Mater. Chem. C 2019, 7, 3082. doi: 10.1039/C8TC06575F
[7]	Zhang, Y.; Zhang, D.; Wei, J.; Hong, X.; Duan, L. Angew. Chem., nt. Ed. 2020, 36, 17499.
[8]	Liu, Y.; Xiao, X.; Ran, Y.; Bin, Z. Y.; You, J. S. Chem. Sci. 2021, 12, 9408. doi: 10.1039/D1SC02042K
[9]	Zhang, Y. W.; Zhang, D. D.; Duan, L. Angew. Chem., nt. Ed. 2019, 58, 16912.
[10]	Wang, Y.; Xu, Y.; Li, C.; Li, Z.; Wei, J. Angew. Chem.,Int. Ed. 2020, 59, 17442. doi: 10.1002/anie.v59.40
[11]	Liu, J. Y.; Zhu, Y. H.; Zhang, Q. S. Nat. Commun. 2022, 13, 4876. doi: 10.1038/s41467-022-32607-3
[12]	Yang, M.; Park, I. S.; Yasuda, T. J. Am. Chem. Soc. 2020, 142, 19468. doi: 10.1021/jacs.0c10081
[13]	Xu, Y. C.; Zhang, Z. L.; Wang, Y. Adv. Opt. Mater. 2020, 8, 1902142. doi: 10.1002/adom.v8.9
[14]	Ning, W. M.; Wang, H.; Gong, S. L.; Zhong, C.; Yang, C. L. Sci. China: Chem. 2022, 65, 1715. doi: 10.1007/s11426-022-1318-9
[15]	Cao, X. S.; Pan, K.; Miao, J. S.; Lv, X. L.; Huang, Z. Y.; Wei, Y. X.; Yang, C. L. Nat. Photonics 2022, 16, 803. doi: 10.1038/s41566-022-01083-y
[16]	Hu, Y. X.; Miao, J. S.; Hua, T.; Huang, Z. Y.; Qi, Y. Y.; Yang, C. L. J. Am. Chem. Soc. 2022, 144, 22976. doi: 10.1021/jacs.2c09543
[17]	Suresh, S. M.; Duda, E.; Hall, D.; Yao, Z.; Zysman-Colman, E. J. Am. Chem. Soc. 2020, 142, 6588. doi: 10.1021/jacs.9b13704
[18]	Zhang, Y.; Wei, J.; Zhang, D.; Yin, C.; Li, G.; Liu, Z. Angew. Chem., nt. Ed. 2020, 59, 17499.
[19]	Suresh, S. M.; Hall, D.; Zhang, M.; Si, C.; Cordes, D. B. Mater. Chem. Front. 2020, 4, 2018. doi: 10.1039/D0QM00190B
[20]	Yuan, Y.; Tang, X.; Du, X. Y.; Hu, Y.; Yu, Y. J.; Jiang, Z. Q.; Liao, L. S.; Lee, S. Adv. Opt. Mater. 2019, 7, 1801536. doi: 10.1002/adom.v7.7
[21]	Liang, X.; Yan, Z. P.; Han, H. B.; Wu, Z. G.; Zheng, Y. X.; Hong, M. Angew. Chem., nt. Ed. 2018, 57, 11316.
[22]	Kondo, Y.; Yoshiura, K.; Kitera, S.; Nishi, H.; Hatakeyama, T. Nat. Photonics 2019, 13, 678. doi: 10.1038/s41566-019-0476-5
[23]	Liu, G.; Sasabe, H.; Kumada, K.; Matsunaga, A.; Katagiri, H.; Kido, J. J. Mater. Chem. C 2021, 9, 8308. doi: 10.1039/D1TC01427G
[24]	Wu, Y.; Zhu, Y.; Zhang, Z.; Zhao, C.; He, J.; Yan, C.; Meng, H.; Mukherjee, S.; Shang, C.; Chen, X. Molecules 2022, 27, 348. doi: 10.3390/molecules27020348
[25]	Matsui, K.; Oda, S.; Yoshiura, K.; Nakajima, K.; Yasuda, N.; Hatakeyama, T. J. Am. Chem. Soc. 2018, 140, 1195. doi: 10.1021/jacs.7b10578 pmid: 29120174
[26]	Park, J.; Lim, J.; Jin, H. L.; Jang, B.; Ju, H. H.; Yoon, S. S. ACS Appl. Mater. Interfaces 2021, 13, 45798. doi: 10.1021/acsami.1c11399
[27]	Park, I. S.; Min, H.; Kim, J. U.; Yasuda, T. Adv. Opt. Mater. 2021, 9, 2101282. doi: 10.1002/adom.v9.24
[28]	Park, I.; Yang, M.; Shibata, H.; Amanokura, N.; Yasuda, T. Adv. Mater. 2022, 34, 2107951. doi: 10.1002/adma.v34.9
[29]	Ji, H.; Wjc, B.; Jk, A.; Jyl, B. Mater. Today Energy 2021, 21, 100792.
[30]	Tanaka, H.; Oda, S.; Ricci, G.; Gotoh, H.; Tabata, K.; Kawasumi, R.; Beljonne, D.; Olivier, Y; Hatakeyama, T. Angew. Chem.,Int. Ed. 2021, 60, 17910. doi: 10.1002/anie.v60.33
[31]	Im, Y.; Si, H. H.; Lee, J. Y. J. Mater. Chem. C 2018, 6, 5012. doi: 10.1039/C8TC00546J
[32]	Lee, Y. H.; Jung, J.; Yoo, S.; Lee, M. H. Adv. Opt. Mater. 2018, 6, 1800385. doi: 10.1002/adom.v6.17
[33]	Cui, L. S.; Nomura, H.; Geng, Y.; Kim, J. U.; Adachi, C. Angew. Chem., nt. Ed. 2017, 56, 1571.
[34]	Lee, Y. H.; Lee, D.; Lee, T.; Lee, J.; Min, H. L. Dyes Pigm. 2021, 188, 109224. doi: 10.1016/j.dyepig.2021.109224
[35]	Xia, G. Q.; Qu, C.; Zhu, Y. L.; Ye, J. J.; Ye, K. Q.; Zhang, Z. L.; Wang, Y. Angew. Chem., nt. Ed. 2021, 60, 9598.
[36]	Lim, H.; Cheon, H. J.; Woo, S. J.; Kwon, S. K.; Kim, Y. H.; Kim, J. J. Adv. Mater. 2020, 2004083.
[37]	Wang, T. T.; Hua, X. C.; Yu, Y. J.; Yuan, Y.; Feng, M. Q.; Jiang, Z. Q. Chin. J. Org. Chem. 2019, 39, 1436. (in Chinese) doi: 10.6023/cjoc201810016
	(王彤彤, 华晓晨, 郁友军, 袁熠, 冯敏强, 蒋佐权, 有机化学, 2019, 39, 1436.) doi: 10.6023/cjoc201810016
[38]	Zhang, Q.; Kuwabara, H.; Potscavage, W. J.; Huang, S.; Hatae, Y.; Shibata, T.; Adachi, C. J. Am. Chem. Soc. 2014, 136, 18070. doi: 10.1021/ja510144h
[39]	Yang, H. Y.; Zhang, M.; Zhao, J. W.; Pu, C. P.; Lin, H.; Tao, S. L.; Zheng, C. J.; Zhang, X. H. Chin. J. Chem. 2022, 40, 911. doi: 10.1002/cjoc.v40.8
[40]	Northey, T.; Penfold, T. J. Org. Electron. 2018, 59, 45. doi: 10.1016/j.orgel.2018.04.038
[41]	Oda, S.; Kawakami, B.; Kawasumi, R.; Okita, R.; Hatakeyama, T. Org. Lett. 2019, 21, 9311. doi: 10.1021/acs.orglett.9b03342
[42]	Paterson, L.; Mondal, A.; Heimel, P.; Lovrincic, R.; May, F.; Lennartz, C. Nat. Commun. 2019, 9, 4990. doi: 10.1038/s41467-018-07432-2