High-efficiency Near Infrared Thermally Activated Delayed Fluorescence Based on Phenazine Acceptor

doi:10.6023/A24100310

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (1): 17-24.DOI: 10.6023/A24100310 Previous Articles Next Articles

Original article

基于吩嗪受体单元的高效近红外热激活延迟荧光

马金珠^a, 李阳^a, 高珊^a, 赵越^b, 丁磊^c^,^*(), 周东营^a^,^*(), 樊健^a^,^*()

a 苏州大学功能纳米与软物质研究院江苏省碳基功能材料与器件重点实验室苏州 215123
b 南京大学配位化学研究所配位化学国家重点实验室南京 210023
c 苏州科技大学化学与生命科学学院苏州 215127

投稿日期:2024-10-17 发布日期:2024-12-25
基金资助:
国家重点研发计划(2020YFA0714604); 国家自然科学基金(22005184); 国家自然科学基金(62375193); 江苏省国际科技合作/港澳台科技合作项目(BZ2023053)

High-efficiency Near Infrared Thermally Activated Delayed Fluorescence Based on Phenazine Acceptor

Jinzhu Ma^a, Yang Li^a, Shan Gao^a, Yue Zhao^b, Lei Ding^c(), Dongying Zhou^a(), Jian Fan^a()

a Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of Functional Nano & Soft Materials, Soochow University, Suzhou 215123, China
b State Key Laboratory of Coordination Chemistry, Institute of Coordination Chemistry, Nanjing University, Nanjing 210023, China
c School of Chemistry and Life Sciences, Suzhou University of Science and Technology, Suzhou 215127, China

Received:2024-10-17 Published:2024-12-25
Contact: *E-mail: dinglei@usts.edu.cn; dyzhou@suda.edu.cn; jianfan@suda.edu.cn
Supported by:
National Key R&D Program of China(2020YFA0714604); National Natural Science Foundation of China(22005184); National Natural Science Foundation of China(62375193); International Science and Technology Innovation Cooperation/Hong Kong, Macao and Taiwan Science and Technology Innovation Cooperation Project of Jiangsu Province(BZ2023053)

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Abstract

Two donor-acceptor-donor (D-A-D) type red thermally activated delayed fluorescence (TADF) materials 10,13- bis(4-(diphenylamino)phenyl)dibenzo[a,c]phenazine-3,6-dicarbonitrile (BzPz-TPA) and 10,13-bis(4-(diphenylamino)phenyl)- dipyrido[3,2-a:2',3'-c]phenazine-11,12-dicarbonitrile (PyPz-TPA) were designed and synthesized with dibenzophenazine and dipyridobenzazine as acceptor units and triphenylamine as donor units respectively. Two cyano groups were introduced into BzPz-TPA and PyPz-TPA to enhance the electron-withdrawing capability of the acceptor unit. Strong donor and acceptor units were introduced into the molecular skeletons of BzPz-TPA and PyPz-TPA, and steric hindrance between D and A units led to a twisted D-A configuration, thus achieving relatively small singlet-triplet energy gaps (ΔE_ST). In addition, the intramolecular hydrogen bonding interaction between donor and acceptor units can modulate the D-A molecular configuration and the overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). In the BzPz-TPA molecule, the dihedral angle between the donor and acceptor units is 44°, and there is a twisted configuration between D-A, thereby achieving effective separation of HOMO and LUMO. HOMO is mainly located on the donor unit TPA, while LUMO is mainly located on the acceptor unit. In PyPz-TPA molecule, the dihedral angle between the donor and acceptor units is 52°, and the D-A twisted configuration effectively separates the HOMO and LUMO. The HOMO is mainly on the donor unit TPA, and the LUMO is mainly on the acceptor unit. Since BzPz-TPA and PyPz-TPA have the same donor unit, they have similar HOMO energy levels. Due to the rigid skeleton of two molecules and the smaller ΔE_ST, the BzPz-TPA is doped into the host material 4,4'-bis(9-carbazole)biphenyl (CBP) and resulted in the maximum external quantum efficiency (EQE) of 7.4% for the organic light-emitting diode (OLED) device emitting at 638 nm. When PyPz-TPA is doped into the host material CBP, the OLED device achieved the maximum EQE of 22.6% at 676 nm emission. Besides, the OLED of PyPz-TPA achieved the maximum EQE of 16.58% and near-infrared luminescence at an emission wavelength of 714 nm.

Key words: thermally activated delayed fluorescence, singlet-triplet energy gap, external quantum efficiency, thermal stability, electroluminescence performance

Cite this article

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.

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Fig. & Tab. 7

Scheme 1. Synthetic route of PyPz-TPA and BzPz-TPA

Figure 1. Electronic cloud distribution of BzPz-TPA

Figure 2. Electronic cloud distribution of PyPz-TPA

Figure 3. Normalized UV-vis absorption, fluorescence spectra at room temperature and 77 K, phosphorescence spectra at 77 K in toluene of BzPz-TPA (a) and PyPz-TPA (b)

化合物	λ_abs^a/nm		λ_em^a/nm		Φ_{PL, tol}^a/%		PL_fl/ph^b/nm		(T_g/T_d)^c/℃		(HOMO/LUMO)^d/eV		E_g^e/eV				(E_S1/E_T1)^f/eV	ΔE_ST^g/eV
BzPz-TPA		346/525		650		94.0		595/688		n.a./491	－5.22/－3.13		2.09		2.08/1.80			0.28
PyPz-TPA		345/564		667		86.0		642/714		303/456		－5.12/－3.17		1.95		1.93/1.74			0.19

Table 1. Summary of the physical properties of BzPz-TPA and PyPz-TPA

发光材料	掺杂比(w/%)	电压^a/V	CE^b/(cd•A⁻¹)	PE^b/(lm•W⁻¹)	EQE^b/%	λ^b/nm
BzPz-TPA	1	3.3	7.0	6.7	7.39	638
	2	3.2	5.3	5.1	7.05	642
	4	3.3	3.2	3.1	6.33	654
	8	3.0	1.6	1.7	5.68	664
PyPz-TPA	1	3.3	6.1	6.0	22.56	676
	2	3.3	3.1	3.0	20.64	686
	4	3.2	1.6	1.6	20.74	700
	8	3.2	0.7	0.7	16.58	714

Table 2. EL performance of BzPz-TPA and PyPz-TPA based OLEDs

Figure 4. Normalized EL performance of BzPz-TPA and PyPz-TPA based OLEDs. (a), (d) Normalized EL spectra curves of the BzPz-TPA and PyPz-TPA. (b), (e) External quantum efficiency (EQE)-current density characteristics of the BzPz-TPA and PyPz-TPA. (c), (f) Current density-voltage- luminance characteristics of BzPz-TPA and PyPz-TPA

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基于吩嗪受体单元的高效近红外热激活延迟荧光

High-efficiency Near Infrared Thermally Activated Delayed Fluorescence Based on Phenazine Acceptor

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Fig. & Tab. 7

References 32

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