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

doi:10.6023/cjoc202303022

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (11): 3876-3887.DOI: 10.6023/cjoc202303022 Previous Articles Next Articles

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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Abstract

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

Cite this article

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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Fig. & Tab. 16

Scheme 1. Synthetic route of compounds 3 and 4

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

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

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

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

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

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

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)

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

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

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

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

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

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

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

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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Fig. & Tab. 16

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