Xanthone Based Thermally Activated Delayed Fluorescence Enantiomers for Efficient Circularly Polarized Electroluminescence

doi:10.6023/A25010010

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (5): 471-478.DOI: 10.6023/A25010010 Previous Articles Next Articles

Article

基于呫吨酮电子受体的高效圆偏振热活化延迟荧光材料

方素琴^a^,^†, 童恺宁^b^,^†, 陈思浛^a^,^†, 张千峰^a, 童碧海^a^,^c^,^*(), 冯敏强^b^,^*(), 孔辉^a^,^*()

^a 安徽工业大学冶金工程学院分子工程与应用化学研究所马鞍山 243002
^b 苏州大学功能纳米与软材料研究院江苏省碳基功能材料与器件重点实验室苏州 215123
^c 南京大学配位化学国家重点实验室南京 210023

投稿日期:2025-01-07 发布日期:2025-03-10
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(21572001); 安徽省特支计划(T000609); 皖江学者特聘教授计划

Xanthone Based Thermally Activated Delayed Fluorescence Enantiomers for Efficient Circularly Polarized Electroluminescence

Suqin Fang^a, Kaining Tong^b, Sihan Chen^a, Qianfeng Zhang^a, Bihai Tong^a^,^c^,^*(), Mankeung Fung^b^,^*(), Hui Kong^a^,^*()

^a Institute of Molecular Engineering And Applied Chemistry, School of Metallurgy Engineering, Anhui University of Technology, Maanshan 243002, China
^b Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of Functional Nano & Soft Materials, Soochow University, Suzhou 215123, China
^c State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China

Received:2025-01-07 Published:2025-03-10
Contact: * E-mail: tongbihai@163.com; mkfung@suda.edu.cn; konghui@ahut.edu.cn
About author:
^† These authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(21572001); Anhui Special Support Plan(T000609); Distinguished Professor of the Wanjiang Scholars Project

1. .pdf(1020KB)

Abstract

In order to develop cheap and high-efficient circularly polarized thermally activated delayed fluorescence (CP-TADF) materials, herein, we have designed and synthesized two pairs of chiral enantiomers (R/S)-AOBD and (R/S)-POBD by fusing the H₈-BINOL skeleton into xanthone electron acceptor group. The electron donor groups of 9,10-dihydro-9,9-dimethylacridine or phenoxazine were used to regulate the emission wavelength and properties of materials. The photophysical and chiral optical properties of these materials have been studied. Electroluminescent devices using these materials were prepared by vapor deposition process and their performances were evaluated. Compounds exhibit good thermal stabilities. The decomposition temperatures (T_d) of 5% weight loss are 433 ℃ for AOBD and 452 ℃ for POBD. The glass transition temperatures (T_g) of AOBD and POBD are 152 ℃ and 258 ℃. Their high T_d and T_g can meet the requirements for material thermal stability in the organic light-emitting diodes (OLED) application and vacuum evaporation processes. These materials have moderate photoluminescence quantum efficiencies (0.34~0.43). They have small ∆E_ST (0.051~0.056 eV) and showed obvious aggregation-induced delayed fluorescence activity. The lowest unoccupied molecular orbitals (LUMOs) of these compounds are mostly located on the xanthone groups and the distribution proportion attributed to chiral H₈-BINOL substructures is as high as 28%. Therefore, their photoluminescence (PL) spectra also have obvious circular polarization with dissymmetry factors (|g_PL|) values between 5.4×10^-4 and 9.0×10^-4. The circularly polarized organic light-emitting diodes (CP-OLEDs) using these compounds show good performances with the maximum external quantum efficiency (EQE_max) of 10.6%~16.6% and intense circularly polarized electroluminescence signal with dissymmetry factor (|g_EL|) of 2.2×10^-3~5.4×10^-3. These devices also exhibited high brightness (9118~32010 cd•m^-2) and small efficiency roll-off (18%, at 1000 cd•m^-2). The high performance in device efficiencies and dissymmetry factor of these materials is attributed to the full fusion of the H₈-BINOL units with receptor groups, as well as their steric hindrance effect. It provides a good strategy for the development of stable electroluminescent materials with high efficiency and dissymmetry factor.

Key words: organic light-emitting diodes, circularly polarized luminescence, thermally activated delayed fluorescence, octahydronaphthol, xanthone

Cite this article

Suqin Fang, Kaining Tong, Sihan Chen, Qianfeng Zhang, Bihai Tong, Mankeung Fung, Hui Kong. Xanthone Based Thermally Activated Delayed Fluorescence Enantiomers for Efficient Circularly Polarized Electroluminescence[J]. Acta Chimica Sinica, 2025, 83(5): 471-478.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 10

Figure 1. Synthetic routes of AOBD and POBD (I) Methyl 4-bromo-2-fluorobenzoate, dimethylformamide, K2CO3, 110 ℃, N2, 12 h; (II) KOH, 4-dioxane, r.t., 12 h; (III) Trifluoroacetic acid, Trifluoroacetic anhydride, r.t., 12 h; (IV) Phenoxazine or 9,10-dihydro-9,9-dimethylacridine, t-BuOK, Pd(OAc)2, t-Bu3PHBF4, toluene, 110 ℃, N2, 12 h.

Figure 2. Thermogravimetric analysis plots of AOBD and POBD

Figure 3. UV-Vis absorption and photoluminescence spectra of AOBD and POBD: (a) UV-Vis absorption spectra of AOBD and POBD in CH2Cl2; (b) Photoluminescence spectra of solid and 1% (w) PMMA films

Sample	λ_em^a/nm	Φ^b/%	τ_prompt^b/μs	τ_delayed^b/ns	R_delayed^b/%	∆E_ST ^c/eV	E_1/2^ox^d/V	HOMO^e/eV	LUMO^f/eV	(T_d/T_g)/℃
R-AOBD	559 (489)	34	0.38	24.0	15	0.051	0.559	–5.359	–2.743	433/152
R-POBD	599 (524)	43	1.14	29.8	30	0.056	0.386	–5.186	–2.755	452/258

Table 1. Physical characteristics of AOBD and POBD

Figure 4. Cyclic voltammetry plots of AOBD and POBD

Figure 5. Contour plots of the HOMOs and the LUMOs for AOBD and POBD

Figure 6. CD and CPPL spectra

Figure 7. The device configurations and chemical structures of the materials used

Figure 8. Character curves of AOBD and POBD devices DA (AOBD) and DP (POBD): (a) Electroluminescent spectra; (b) Current density-voltage- luminance curves; (c) Current efficiency-luminance-power efficiency curves; (d) EQE-luminance curves; (e) CPEL spectra; (f) gEL values-wavelength curves

Device (dopant)	λ_EL/nm	V_on^a/V	L^b/(cd•m^-2)	CE^c/(cd•A^-1)	PE^c/(lm•W^-1)	EQE^c/%	CIE^d (x, y)
DA (AOBD)	488	3.8	9118	24.5 (21.4)	18.7 (12.3)	10.6 (8.6)	(0.22, 0.42)
DP (POBD)	548	4.0	32010	53.3 (44.1)	41.7 (24.3)	16.6 (13.7)	(0.41, 0.55)

Table 2. AOBD and POBD device luminescence and efficiency data

References 24

[1]	Yang, X. F.; Gao, X. Q.; Zheng, Y. X.; Kuang, H.; Chen, C. F.; Liu, M. H.; Duan, P. F.; Tang, Z. Y. CCS Chem. 2023, 5, 2760.
[2]	Diksha, T.; Sivakumar, V. J. Mater. Chem. C 2024, 12, 13168.
[3]	Sophie, F.; Mathilde, P.; Longhui, G.; Alaric, D.; Adrian, J. R.; Damien, P.; Denis, T.; Bernard, G.; Gilles, M.; Gilles, C.; Grégory, P. J. Am. Chem. Soc. 2016, 138, 3990.
[4]	Song, F. Y.; Xu, Z.; Zhang, Q. S.; Zhao, Z.; Zhang, H. K.; Zhao, W. J.; Qiu, Z. J.; Qi, C. X.; Zhang, H.; Sung, H. H. Y.; Williams, I. D.; Lam, J. W. Y.; Zhao, Z. J.; Qin, A. J.; Dongge, M.; Tang, B. Z. Adv. Funct. Mater. 2018, 28, 1800051.
[5]	Sun, S. b.; Wang, J.; Chen, L. F.; Chen, R. F.; Jin, J. B.; Chen, C. L.; Chen, S. F.; Xie, G. H.; Zheng, C.; Huang, W. J. Mater. Chem. C. 2019, 7, 14511.
[6]	Lucas, F.; Alaric, D.; Romain, P.; Leonid, L.; Gilles, M.; Cassie, V.; Gilles, C.; Etienne, Q.; Benoit, R.; Sylvia, M. D. G.; Jean-Pierre, D.; Pierre, T.; Jeanne, C.; Ludovic, F.; Grégory, P. Adv. Funct. Mater. 2020, 30, 2004838.
[7]	Wang, Y. X.; Zhang, Y.; Hu, W. R.; Quan, Y. W.; Li, Y. Z.; Cheng, Y. X. ACS Appl. Mater. Interfaces. 2019, 11, 26165.
[8]	Wu, P. F.; Adriana, P.; Mariagrazia, F.; Masayoshi, B.; Katsuhiro, M.; Tatsuya, N.; Shuhei, S.; Hiroyasu, S.; Naofumi, N.; Tamaki, N. Chirality. 2022, 34, 317.
[9]	Frescilia, O. S.; Maike, T.; Rohan, Y.; André, P.; Guido, H. C.; Jochen, N. J. Org. Chem. 2018, 83, 14568.
[10]	Wu, Z. G.; Han, H. B.; Yan, Z. P.; Luo, X. F.; Wang, Y.; Zheng, Y. X.; Zuo, J. L.; Pan, Y. Adv. Mater. 2019, 31, 1900524.
[11]	Wu, Z. G.; Yan, Z. P.; Luo, X. F.; Yuan, L.; Liang, W. Q.; Wang, Y.; Zheng, Y. X.; Zuo, J. L.; Pan, Y. J. Mater. Chem. C. 2019, 7, 7045. doi: 10.1039/c9tc01632e
[12]	Liang, Z. P.; Tang, R.; Qiu, Y. C.; Wang, Y.; Lu, H. B.; Wu, Z. G. Acta Chim. Sinica. 2021, 79, 1401. (in Chinese)
	(梁志鹏, 唐瑞, 邱雨晨, 王阳, 陆洪彬, 吴正光, 化学学报, 2021, 79, 1401.) doi: 10.6023/A21070355
[13]	Liu, T. T.; Yan, Z. P.; Hu, J. J.; Yuan, L.; Luo, X. F.; Tu, Z. L.; Zheng, Y. X. ACS Appl. Mater. Interfaces. 2021, 13, 56413.
[14]	Xu, Y. C.; Wang, Q. Y.; Cai, X. L.; Li, C. L.; Wang, Y. Adv. Mater. 2021, 33, 2100652.
[15]	Xie, F. M.; Zhou, J. X.; Zeng, X. Y.; An, Z. D.; Li, Y. Q.; Han, D. X.; Duan, P. F.; Wu, Z. G.; Zheng, Y. X.; Tang, J. X. Adv. Opt. Mater. 2021, 9, 2100017.
[16]	Wang, Y. F.; Liu, X.; Zhu, Y.; Li, M.; Chen, C. F. J. Mater. Chem. C. 2022, 10, 4805.
[17]	Teng, J. M.; Zhang, D. W.; Wang, Y. F.; Chen, C. F. ACS Appl. Mater. Interfaces. 2022, 14, 1578.
[18]	Zhao, W. L.; Wang, Y. F.; Wan, S. P.; Lu, H. Y.; Li, M.; Chen, C. F. CCS Chem. 2022, 4, 3540.
[19]	Yan, Z. P.; Yuan, L.; Zhang, Y.; Mao, M. X.; Liao, X. J.; Ni, H. X.; Wang, Z. H.; An, Z.; Zheng, Y. X.; Zuo, J. L. Adv. Mater. 2022, 34, 2204253.
[20]	Qu, L.; Xiao, H.; Zhang, B.; Yang, Q.; Song, J.; Zhou, X.; Xu, Z. X.; Xiang, H. Chem. Eng. J. 2023, 471, 144709.
[21]	Lan, X.; Zeng, J. J.; Chen, J. K.; Yang, T.; Dong, X. B.; Tang, B. Z.; Zhao, Z. J. Angew. Chem. Int. Ed. 2025, 137, e202414488.
[22]	Zhao, P.; Guo, W. C.; Li, M.; Lu, H. Y.; Chen, C. F. Angew. Chem. Int. Ed. 2024, 136, e202409020.
[23]	Liu, H. J.; Zeng, J. J.; Guo, J. J.; Nie, H.; Zhao, Z. J.; Tang, B. Z. Angew. Chem., Int. Ed. 2018, 57, 9290.
[24]	Hiroki, U.; Kenichi, G.; Katsuyuki, S.; Hiroko, N.; Chihaya, A. Nature. 2012, 492, 234.

基于呫吨酮电子受体的高效圆偏振热活化延迟荧光材料

Xanthone Based Thermally Activated Delayed Fluorescence Enantiomers for Efficient Circularly Polarized Electroluminescence

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 10

References 24

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jinzhu Ma, Yang Li, Shan Gao, Yue Zhao, Lei Ding, Dongying Zhou, Jian Fan. High-efficiency Near Infrared Thermally Activated Delayed Fluorescence Based on Phenazine Acceptor [J]. Acta Chimica Sinica, 2025, 83(1): 17-24.
[2]	Dengchao Zhang, Jihui Jia, Dong Liang, Xianbao Cai, Yuqing Zhao, Xianglong Hu, Yubing Jiang, Canzhong Lu. Design, Synthesis and Properties of Cu(I) Complexes with a Nitrogen-containing Spirocycle Ligand for Delayed Fluorescence Materials [J]. Acta Chimica Sinica, 2024, 82(8): 887-893.
[3]	Xiaozhen Li, Qingfu Sun. Research Progress of Rare Earth-Based Circularly Polarized Luminescent Materials [J]. Acta Chimica Sinica, 2024, 82(6): 707-730.
[4]	Yuqing Zhao, Dong Liang, Jihui Jia, Rongmin Yu, Can-Zhong Lu. Synthesis and Characterization of an Emissive Ag(I) Complex with a D-A Type Ligand Containing Two Electron-withdrawing Groups [J]. Acta Chimica Sinica, 2024, 82(5): 486-492.
[5]	Yinuo Wang, Shiyang Shao, Lixiang Wang. Recent Advances in Multiple Resonance Organic/Polymer Fluorescent Materials with Narrowband Emission^★ [J]. Acta Chimica Sinica, 2023, 81(9): 1202-1214.
[6]	Fengjie Ge, Kaizhi Zhang, Qingpeng Cao, Hui Xu, Tao Zhou, Wenhao Zhang, Xinxin Ban, Xiaobo Zhang, Na Li, Peng Zhu. Design, Synthesis and Electroluminescence Performance of Flexible Fluorenyl Block Delayed Fluorescence Dimers [J]. Acta Chimica Sinica, 2023, 81(9): 1157-1166.
[7]	Zhenyu Liu, Junfeng Rao, Shoujia Zhu, Bingyang Wang, Fan Yu, Quanyou Feng, Linghai Xie. Research Progress of Solution-Processed Self-Host Thermally Activated Delayed Fluorescence Materials [J]. Acta Chimica Sinica, 2023, 81(7): 820-835.
[8]	Yinfeng Wang, Meng Li, Chuanfeng Chen. Chiral Triptycene-Based Red Thermally Activated Delayed Fluorescence Polymers and Their Organic Light-Emitting Diodes^★ [J]. Acta Chimica Sinica, 2023, 81(6): 588-594.
[9]	Shaoqin Zhang, Meiqing Li, Zhongjun Zhou, Zexing Qu. Theoretical Study on the Multiple Resonance Thermally Activated Delayed Fluorescence Process [J]. Acta Chimica Sinica, 2023, 81(2): 124-130.
[10]	Bin Liu, Pangkuan Chen. Synthesis and Properties of Novel Circularly Polarized Luminescence Materials Based on Binaphthol Skeleton [J]. Acta Chimica Sinica, 2022, 80(7): 929-935.
[11]	Xicheng Feng, Liangliang Zhu, Bingbing Yue. Circularly Polarized Luminescence and Dynamic Regulation Based on the co-Assembly of L/D-Lysine Hydrochloride and Photoactivated AIE Molecules [J]. Acta Chimica Sinica, 2022, 80(5): 647-651.
[12]	Lu Zhou, Jia-Xiong Chen, Shaomin Ji, Wen-Cheng Chen, Yanping Huo. Research Progress of Red Thermally Activated Delayed Fluorescent Materials Based on Quinoxaline [J]. Acta Chimica Sinica, 2022, 80(3): 359-372.
[13]	Longfei Song, Yanyan Zhou, Ting Gao, Pengfei Yan, Hongfeng Li. Point Chirality Regulated Diastereoselective Self-Assembly and Circularly Polarized Luminescence in Eu(III) Triple-Stranded Helicates [J]. Acta Chimica Sinica, 2021, 79(8): 1042-1048.
[14]	Tao Zhou, Yue Qian, Hongjian Wang, Quanyou Feng, Linghai Xie, Wei Huang. Recent Advances in Substituent Effects of Blue Thermally Activated Delayed Fluorescence Small Molecules [J]. Acta Chimica Sinica, 2021, 79(5): 557-574.
[15]	Zhi-Peng Liang, Rui Tang, Yu-Chen Qiu, Yang Wang, Hongbin Lu, Zheng-Guang Wu. Construction and Properties of Octahydrobinaphthol-based Chiral Luminescent Materials with Large Steric Hindrance [J]. Acta Chimica Sinica, 2021, 79(11): 1401-1408.