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

doi:10.6023/cjoc202503029

摘要/Abstract

基于硼和氮原子的多重共振热激活延迟荧光(MR-TADF)分子, 因其窄带发射和高发光效率推动了新一代蓝光有机发光二极管(OLED)的发展. 然而, 典型的MR-TADF分子的平面共轭结构导致分子间聚集, 引发浓度猝灭和光谱展宽, 限制了其应用. 在此, 提出了一种双功能修饰策略, 即在发光核心中引入具有吸电子效应的氟原子和提供位阻效应的苯基基团, 以协同调控分子轨道分布和分子间相互作用. 通过简便的合成方法得到三种MR-TADF材料, 该类材料能有效抑制分子间π-π相互作用, 并实现高效蓝光发射. 对由上述材料制备而成的OLED器件进行性能测试, 结果表明这些材料在高掺杂浓度下均展现良好性能, 特别是N,5,9-三(3,5-二氟-[1,1'-联苯]-2-基)-N-苯基-5,9-二氢-5,9-二氮杂- 13b-硼萘并[3,2,1-de]蒽-7-胺(DFBP-DABAN)的最大外量子效率(EQE_max)达13.3%, 且CIE_y为0.043, 符合蓝光BT.2020标准. 本研究验证了所提出的双功能分子设计策略的有效性, 为实现蓝光MR-TADF材料的开发提供了重要的指导.

关键词: 功能修饰, 硼基多重共振, 蓝光发射, 热激活延迟荧光, 有机发光二极管(OLED)

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)

引用此文

吴建荣, 宋敏, 刘釜铭, 周东营, 廖良生, 蒋佐权. 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[J]. 有机化学, 2025, 45(11): 4152-4162.

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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图/表 8

图式1. 化合物DFBP-DABNA, DFBP-CzDABNA和DFBP-CzDB的合成路线

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

图1. 化合物DFBP-DABNA, DFBP-CzDABNA和DFBP-CzDB的单晶结构及分子堆积图

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

图2. 化合物DFBP-DABNA, DFBP-CzDABNA和DFBP-CzDB的(a)紫外-可见吸收光光谱及荧光发射光谱、(b)低温荧光及磷光光谱及(c, d)瞬态延迟荧光光谱

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

表1. DFBP-DABNA, DFBP-CzDABNA及DFBP-CzDB的光物理性质

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

图3. 化合物DFBP-DABNA, DFBP-CzDABNA和DFBP-CzDB的分子结构和前线分子轨道计算

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

图4. 由化合物DFBP-DABNA, DFBP-CzDABNA和DFBP-CzDB制备的器件的(a, d, g)电致发光峰(EL)、(b, e, f)外量子效率(EQE)及(c, f, i)电流密度-电压-亮度(J-V-L)曲线

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

表2. 化合物DFBP-DABNA, DFBP-CzDABNA及DFBP-CzDB相应制备器件的性能

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

图5. DFBP-DABNA (w=10%), DFBP-CzDABNA (w=15%)和DFBP-CzDB (w=15%)器件的电致光谱的CIE坐标图

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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