Bifunctional Modification Strategy for Constructing Boron-Based Multi-resonance Thermally Activated Delayed Fluorescence Materials with Blue Emission

doi:10.6023/cjoc202503029

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (11): 4152-4162.DOI: 10.6023/cjoc202503029 Previous Articles Next Articles

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双功能修饰策略构建蓝光发射的硼基多重共振热激活延迟荧光材料

吴建荣^a, 宋敏^a, 刘釜铭^a, 周东营^a, 廖良生^a^,^b, 蒋佐权^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江苏苏州 215213
^b 澳门科技大学澳门材料科学与工程研究院澳门材料科学与工程研究院澳门 999078

收稿日期:2025-03-28 修回日期:2025-06-12 发布日期:2025-08-18
基金资助:
国家自然科学基金(22175124); 国家自然科学基金(62175171); 国家自然科学基金(61961160731); 江苏省自然科学基金(BK20220057)

Bifunctional Modification Strategy for Constructing Boron-Based Multi-resonance Thermally Activated Delayed Fluorescence Materials with Blue Emission

Jianrong Wu^a, Min Song^a, Fuming Liu^a, Dongying Zhou^a, Liangsheng Liao^a^,^b, Zuoquan Jiang^a^,^*()

^a Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Institute of Functional Nano & Soft Materials, Soochow University, Suzhou, Jiangsu 215123
^b Macao Institute of Materials Science and Engineering, Macau University of Science and Technology, Macau 999078

Received:2025-03-28 Revised:2025-06-12 Published:2025-08-18
Contact: *E-mail: zqjiang@suda.edu.cn
Supported by:
National Natural Science Foundation of China(22175124); National Natural Science Foundation of China(62175171); National Natural Science Foundation of China(61961160731); the Natural Science Foundation of Jiangsu Province(BK20220057)

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Abstract

Multi-resonance thermally activated delayed fluorescent (MR-TADF) molecules based on boron and nitrogen atoms have promoted the development of a new generation of blue organic light-emitting diodes (OLEDs) due to their narrowband emission and high luminescence efficiency. However, the inherently planar conjugated structure of typical MR- TADF molecules leads to intermolecular aggregation, resulting in concentration quenching and spectral broadening, which restricts their application. Here, a bifunctional modification strategy by introducing fluorine atoms with an electron- withdrawing effect and phenyl groups with a steric hindrance effect into the luminescent core to synergistically regulate molecular orbital distribution and intermolecular interactions is proposed. Three MR-TADF materials were obtained by a simple synthesis method to effectively suppress the intermolecular π-π interaction and achieve efficient blue emission. The corresponding OLED devices incorporating these materials exhibited excellent performance at high doping concentrations. Notably, the device based on N,5,9-tris(3,5-difluoro-[1,1'-biphenyl]-2-yl)-N-phenyl-5,9-dihydro-5,9-diazido-13b-boronaphtho- [3,2,1-de]anthracene-7-amine (DFBP-DABNA) achieved a maximum external quantum efficiency (EQE_max) of 13.3%, with a CIE_y value of 0.043, meeting the BT.2020 blue emission standard. This study demonstrates the effectiveness of the proposed bifunctional molecular design strategy and provides valuable insights for the development of blue emission MR-TADF materials.

Key words: functional modification, boron-based multiple resonance, blue emission, thermally activated delayed fluore- scence, organic light-emitting diode (OLED)

Cite this article

Jianrong Wu, Min Song, Fuming Liu, Dongying Zhou, Liangsheng Liao, Zuoquan Jiang. Bifunctional Modification Strategy for Constructing Boron-Based Multi-resonance Thermally Activated Delayed Fluorescence Materials with Blue Emission[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4152-4162.

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Fig. & Tab. 8

Scheme 1. Synthetic routes of compounds DFBP-DABNA, DFBP-CzDABNA and DFBP-CzDB

Figure 1. Single crystal structures and molecular stacking diagrams of compounds DFBP-DABNA, DFBP-CzDABNA and DFBP-CzDB

Figure 2. (a) UV-Vis absorption spectra and fluorescence emission spectra, (b) low-temperature fluorescence and phosphorescence spectra, and (c, d) transient delayed fluorescence spectra of compounds DFBP-DABNA, DFBP-CzDABNA and DFBP-CzDB

Emitter	λ_abs^a/nm	λ_em^b/nm	FWHM^b/nm	ΔE_ST^c/eV	HOMO^d/eV	LUMO^d/eV	k_RISC^e/(10⁵ s^－1)	PLQY^e/%	T_d/℃
DFBP-DABNA	417	439	23	0.14	－5.27	－2.41	0.40	88	390
DFBP-CzDABNA	433	454	22	0.14	－5.36	－2.62	0.85	89	411
DFBP-CzDB	442	456	18	0.12	－5.34	－2.61	1.39	92	455

Table 1. Photophysical properties of DFBP-DABAN, DFBP-CzDABNA and DFBP-CzDB

Figure 3. Molecular structures and frontier molecular orbital calculations of compounds DFBP-DABNA, DFBP-CzDABNA and DFBP-CzDB

Figure 4. (a, d, g) Electroluminescence (EL) spectra, (b, e, h) external quantum efficiency (EQE) characteristics, and (c, f, i) current density-voltage-luminance (J-V-L) curves of the devices fabricated from the corresponding compounds DFBP-DABNA, DFBP- CzDABNA and DFBP-CzDB

Device	Doping ratio/%	V_on^a/V	λ_EL^b/nm	FWHM^c/nm	CIE^d (x, y)	EQE_max^e/%
DFBP-DABNA	5	3.4	440	35	0.151, 0.038	9.8
	10	3.2	444	35	0.149, 0.043	13.3
	15	3.1	444	35	0.149, 0.047	12.2
	20	3.1	444	37	0.149, 0.051	11.4
DFBP-CzDABNA	5	3.2	460	33	0.134, 0.084	13.1
	10	3.2	460	33	0.132,0.089	15.0
	15	3.2	460	33	0.132, 0.097	17.6
	20	3.1	460	34	0.132, 0.133	16.6
DFBP-CzDB	5	3.2	464	30	0.126, 0.123	10.8
	10	3.2	468	31	0.123, 0.124	15.1
	15	3.2	468	32	0.123, 0.134	19.1
	20	3.1	468	32	0.123, 0.138	18.7

Table 2. Performance of devices prepared from compounds DFBP-DABNA, DFBP-CzDABNA and DFBP-CzDB.

Figure 5. CIE coordinates of EL emission from DFBP-DABNA (w=10%), DFBP-CzDABNA (w=15%) and DFBP-CzDB (w=15%) devices

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双功能修饰策略构建蓝光发射的硼基多重共振热激活延迟荧光材料

Bifunctional Modification Strategy for Constructing Boron-Based Multi-resonance Thermally Activated Delayed Fluorescence Materials with Blue Emission

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