苯并噻唑酮类热活化延迟荧光材料的合成及其光电性能研究

doi:10.6023/cjoc202303022

有机化学 ›› 2023, Vol. 43 ›› Issue (11): 3876-3887.DOI: 10.6023/cjoc202303022 上一篇下一篇

研究论文

苯并噻唑酮类热活化延迟荧光材料的合成及其光电性能研究

张越华^a^,^c^,^d, 聂飞^c^,^d, 周路^c^,^d, 王晓烽^c^,^d, 刘源^c^,^d^,^*(), 霍延平^c^,^e, 陈文铖^c^,^d^,^*(), 赵祖金^b^,^*()

a 广州城市职业学院广州 510405
b 华南理工大学发光材料与器件国家重点实验室广州 510640
c 广东工业大学轻工化工学院广州 510006
d 化学与精细化工广东省实验室揭阳分中心广东揭阳 515200
e 广东工业大学分析测试中心广州 510006

收稿日期:2023-03-15 修回日期:2023-05-30 发布日期:2023-07-12
基金资助:
国家自然科学基金(U2001222); 国家自然科学基金(U22A20399); 国家自然科学基金(52003058); 国家自然科学基金(21975055); 广东省基础与应用基础研究基金(2019B1515120035); 广东省基础与应用基础研究基金(2021A1515010607)

Synthesis and Optoelectronic Studies of Thermally Activated Delayed Fluorescence Materials Based on Benzothiazolyl Ketones

Yuehua Zhang^a^,^c^,^d, Fei Nie^c^,^d, Lu Zhou^c^,^d, Xiaofeng Wang^c^,^d, Yuan Liu^c^,^d(), Yanping Huo^c^,^e, Wencheng Chen^c^,^d(), Zujin Zhao^b()

a Guangzhou City Polytechnic, Guangzhou 510405
b State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640
c School of Light Industry and Chemical Engineering, Guangdong University of Technology, Guangzhou 510006
d Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory, Jieyang, Guangdong 515200
e Analysis and Test Center, Guangdong University of Technology, Guangzhou 510006

Received:2023-03-15 Revised:2023-05-30 Published:2023-07-12
Contact: * E-mail: liuyuancc@gdut.edu.cn; wencchen@gdut.edu.cn; mszjzhao@scut.edu.cn
Supported by:
National Natural Science Foundation of China(U2001222); National Natural Science Foundation of China(U22A20399); National Natural Science Foundation of China(52003058); National Natural Science Foundation of China(21975055); Guangdong Basic and Applied Basic Research Foundation(2019B1515120035); Guangdong Basic and Applied Basic Research Foundation(2021A1515010607)

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摘要/Abstract

以苯并噻唑-2-基(苯基)甲酮作为受体, 具有强给电子能力的吩噁嗪和吩噻嗪作为给体构筑给体-受体(D-A)型分子, 设计合成了两种具有聚集诱导发光(AIE)特性的热活化延迟荧光(TADF)红光材料3和4, 并对它们的热稳定性、电化学性质、单晶结构、光物理性质和电致发光性能进行了系统研究. 两种化合物具有较小的单三线态能级差(ΔE_ST, 0.04和0.16 eV)以及微秒级延迟寿命(0.63和1.30 μs), 表现出明显的TADF特性. 通过对比化合物在粉末状态下研磨前后的发射光谱, 发现化合物4具有明显的力致变色发光现象. 在纯薄膜下, 两种化合物的发射峰分别为683和654 nm, 光致发光量子产率(PLQY)分别为0.8%和3.6%. 基于化合物3和4的非掺杂有机发光二极管(OLED)器件, 均获得了纯红光发射(662和652 nm), 器件的最大外量子效率(EQE)分别为0.15%和0.34%. 虽然基于这两种化合物的器件发光效率有待提升, 但它们的合成过程简便, 能为开发苯并噻唑酮类TADF红光材料提供一定的启发.

关键词: 聚集诱导发光(AIE)特性, 热活化延迟荧光(TADF)红光材料, 力致变色发光, 苯并噻唑酮类

Two thermally activated delayed fluorescence (TADF) red-emitting materials 3 and 4 with aggregation-induced emission (AIE) properties were designed and synthesized using benzothiazole-2-yl(phenyl)methanone as acceptors, and phenoxazine and phenothiazine with strong electron-donating ability as donors to construct donor-acceptor (D-A) type molecules, and their thermal stability, electrochemical properties, single crystal structure, photophysical properties and electroluminescence properties were systematically studied. The two compounds have small singlet-triplet slitting (ΔE_ST, 0.04 and 0.16 eV) and microsecond-scale delayed lifetimes (0.63 and 1.30 μs), showing obvious TADF characteristics. Comparing the emission spectra before and after grinding in the powder state, it is found that compound 4 has obvious mechanochromic luminescence phenomenon. In neat-film state, the emission peaks of the two compounds were 683 and 654 nm, and photoluminescence quantum yields (PLQYs) were 0.8% and 3.6%, respectively. The non-doped organic light-emitting diode (OLED) devices based on compounds 3 and 4 obtained pure red emission (662 and 652 nm), and the maximum external quantum efficiencies (EQEs) of the devices were 0.15% and 0.34%, respectively. Although the luminous efficiencies of devices based on these two compounds are not high, their synthesis process is facile, which can provide useful insight for the development of red TADF materials based on benzothiazolyl ketones.

Key words: aggregation-induced emission (AIE) property, thermally activated delayed fluorescence (TADF) red light material, mechanochromic luminescence, benzothiazolyl ketones

引用此文

张越华, 聂飞, 周路, 王晓烽, 刘源, 霍延平, 陈文铖, 赵祖金. 苯并噻唑酮类热活化延迟荧光材料的合成及其光电性能研究[J]. 有机化学, 2023, 43(11): 3876-3887.

Yuehua Zhang, Fei Nie, Lu Zhou, Xiaofeng Wang, Yuan Liu, Yanping Huo, Wencheng Chen, Zujin Zhao. Synthesis and Optoelectronic Studies of Thermally Activated Delayed Fluorescence Materials Based on Benzothiazolyl Ketones[J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3876-3887.

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图/表 16

图式1. 化合物3和4的合成路线

Scheme 1. Synthetic route of compounds 3 and 4

图1. 化合物3和4构型优化下的HOMO和LUMO能级、电子云分布

Figure 1. HOMO and LUMO energy levels and electron cloud distribution under the configuration optimization of compounds 3 and 4

图2. 化合物3的单晶结构(a)、堆积方式(b)、分子间π-π相互作用(c, d)

Figure 2. Single crystal structure (a), packing pattern (b), and intermolecular π-π interactions (c, d) of compound 3

图3. 化合物4的单晶结构(a)、几何结构参数(b)、堆积方式(c)、分子间π-π相互作用(d)

Figure 3. Single crystal structure (a), geometric structure parameters (b), packing pattern (c), intermolecular π-π interactions (d) of compound 4

图4. 室温下化合物3和4在甲苯溶剂中的归一化紫外可见吸收光谱和在不同溶剂中的荧光发射光谱

Figure 4. Normalized UV-Vis absorption spectra in toluene solvent and fluorescence spectra in different solvents of compounds 3 and 4 at room temperature

Compd.	λ_abs/nm	λ_PL/nm	PLQY/%	τ_p/ns	τ_d/μs	T_d/T_g	E_S1/E_T1	E_HOMO/E_LUMO
3	317/458^a	586^a, 683^b, 630^c	0.8^b, 10.0^c	9.15^c	0.63^c	338/57	2.26/2.22^c	–5.15/–2.91^d
4	304/389^a	440/605^a, 654^b, 609^c	3.6^b, 45.9^c	21.8^c	1.30^c	351/66	2.69/2.53^c	–5.14/–2.33^d

表1. 化合物3和4的光物理数据汇总

Table 1. Summary of photophysical data of compounds 3 and 4

图5. 化合物3 (a)和4 (b)在不同比例THF和水混合体系中的发射光谱

Figure 5. Emission spectra of compounds 3 (a) and 4 (b) in THF and water mixed systems with different proportions

图6. 室温下化合物3 (a)和4 (b)重结晶的固体研磨前后荧光光谱的对比、两种化合物研磨前后在365 nm紫外灯照射下颜色的变化(c)

Figure 6. Comparison of fluorescence spectra of compounds 3 (a) and 4 (b) recrystallized solids before and after grinding at room temperature, and color changes of the two compounds before and after grinding under 365 nm UV lamp irradiation (c)

图7. 室温下化合物3和4在纯薄膜和掺杂薄膜状态下的归一化荧光发射光谱

Figure 7. Normalized fluorescence emission spectra of compounds 3 and 4 in neat and doped thin films at room temperature

图8. 77 K下化合物3 (a)和4 (b)在掺杂薄膜状态下的归一化荧光和磷光光谱

Figure 8. Normalized fluorescence and phosphorescence spectra of compounds 3 (a) and 4 (b) in doped thin films at 77 K

图9. 化合物3 (a)和4 (b)在掺杂薄膜状态下的延迟发射瞬态PL衰减曲线

Figure 9. Transient PL decay curves of delayed emission of compounds 3 (a) and 4 (b) in doped thin films

Temperature/K	τ_p/ns		τ_d/μs		Ratio/%
Temperature/K	3	4	3	4	3	4
300	9.15	21.8	0.63	1.30	68/32	48/52
200	9.45	26.6	0.94	1.50	66/34	54/46
100	8.43	28.0	1.17	1.39	61/38	68/32

表2. 化合物3 (a)和4 (b)在掺杂薄膜状态下的瞬态(τp)和延迟(τd)组分的PL寿命

Table 2. PL lifetimes of transient (τp) and delayed (τd) components of compounds 3 (a) and 4 (b) in doped thin films

图10. 化合物3 (a)和4 (b)在氩气、空气和氧气条件下在正己烷中的发射光谱

Figure 10. Emission spectra of compounds 3 (a) and 4 (b) in n-hexane under argon, air and oxygen

图11. 非掺杂器件(a)和掺杂器件(b)的能级图及器件中所用材料的化学结构(c)

Figure 11. Energy level diagrams of undoped devices (a) and doped devices (b), and chemical structure (c) of materials used in devices

图12. 器件的电致发光光谱(a)、J-V-L特性曲线(b)、EQE-J特性曲线(c)和EQE-L特性曲线(d)

Figure 12. Electroluminescence spectrum (a), J-V-L characteristic curve (b), EQE-J characteristic curve (c) and EQE-L characteristic curve (d) of the device

Device	V_on/V	L_max/(cd•m^–2)	Maximum value/the value at 1000 cd•m^–2			λ_EL/nm	CIE (x, y)	Roll-off of EQE/%
Device	V_on/V	L_max/(cd•m^–2)	CE/(cd•A^–1)	PE/(lm•W^–1)	EQE/%	λ_EL/nm	CIE (x, y)	Roll-off of EQE/%
A	4.0	283	0.11/—	0.07/—	0.15/—	662	(0.604, 0.364)	—
B	3.8	2729	1.48/1.17	1.11/0.51	1.10/0.87	620	(0.585, 0.412)	20.9
C	3.8	971	3.58/—	2.96/—	2.15/—	612	(0.563, 0.432)	—
D	3.8	1459	5.47/2.54	5.46/0.91	2.77/1.29	600	(0.539, 0.454)	53.4
E	3.4	26680	10.14/9.11	8.65/6.22	4.42/4.00	589	(0.505, 0.480)	9.5
F	4.2	971	0.20/—	0.15/—	0.34/—	652	(0.609, 0.380)	—
G	3.6	5073	3.40/2.50	2.80/1.2	1.80/1.30	604	(0.500, 0.455)	27.8
H	3.8	1164	5.16/1.61	4.27/0.50	2.62/0.82	604	(0.499, 0.456)	68.7
I	3.6	1208	7.56/1.77	6.59/0.59	3.45/0.81	589	(0.478, 0.463)	76.5
J	3.4	13950	10.42/4.46	9.63/2.92	4.62/2.00	584	(0.425, 0.461)	56.7

表3. 基于两种化合物的电致发光数据汇总

Table 3. Summary of electroluminescence data based on two compounds

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苯并噻唑酮类热活化延迟荧光材料的合成及其光电性能研究

Synthesis and Optoelectronic Studies of Thermally Activated Delayed Fluorescence Materials Based on Benzothiazolyl Ketones

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