基于呫吨酮电子受体的高效圆偏振热活化延迟荧光材料

doi:10.6023/A25010010

化学学报 ›› 2025, Vol. 83 ›› Issue (5): 471-478.DOI: 10.6023/A25010010 上一篇下一篇

研究论文

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

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1. Supporting Information-A25010010.pdf(1020KB)

摘要/Abstract

为了开发低成本、高效率的圆偏振热活化延迟荧光(CP-TADF)材料, 将八氢联萘酚(H₈-BINOL)骨架与呫吨酮电子受体基团充分融合, 合成了两对手性对映异构体(R/S)-AOBD和(R/S)-POBD. 利用9,10-二氢-9,9-二甲基吖啶或吩噁嗪电子供体基团来调节材料的发射波长和性质, 本工作研究了这些材料的光物理性质和手性光学性质, 采用气相沉积法制备了这些材料的电致发光器件, 并对其性能进行了研究. 两种化合物均表现出良好的热稳定性. 减重5%的分解温度(T_d) AOBD为433 ℃, POBD为452 ℃. AOBD和POBD的玻璃化转变温度(T_g)分别为152和258 ℃. 它们的高T_d和T_g可以满足在有机发光二极管(OLED)应用和真空蒸发过程中对材料热稳定性的要求. 其光致发光量子效率在0.34~0.43之间, 具有较小的∆E_ST (0.051~0.056 eV)和显著的聚集诱导延迟荧光活性. 两种化合物的最低未占据分子轨道(LUMO)主要分布在呫吨酮基团上, 其中在H₈-BINOL亚结构上的分布比例高达28%, 它们的光致发光光谱也具有明显的圆极化, 不对称因子(|g_PL|)值在5.4×10^-4和9.0×10^-4之间. 用这些化合物制备的圆偏振有机发光二极管(CP-OLEDs)具有良好的性能, 其掺杂器件的外量子效率最高可达16.6%, 不对称因子(|g_EL|)在2.2×10^-3~5.4×10^-3之间, 器件亮度在9118~32010 cd•m^-2之间, 亮度在1000 cd•m^-2时的效率滚降仅为18%. 这些材料的高效率和高不对称因子归因于H₈-BINOL单元与受体基团的完全融合以及它们的空间位阻效应, 为开发兼具高效率和高不对称因子的稳定电致发光材料提供了一个很好的思路.

关键词: 有机发光二极管, 圆偏振发光, 热激活延迟荧光, 八氢联萘酚, 呫吨酮

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

引用此文

方素琴, 童恺宁, 陈思浛, 张千峰, 童碧海, 冯敏强, 孔辉. 基于呫吨酮电子受体的高效圆偏振热活化延迟荧光材料[J]. 化学学报, 2025, 83(5): 471-478.

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.

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图/表 10

图1. AOBD和POBD的合成路线

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.

图2. AOBD和POBD的热重分析图

Figure 2. Thermogravimetric analysis plots of AOBD and POBD

图3. AOBD和POBD的紫外-可见吸收和光致发光光谱: (a) CH2Cl2中AOBD和POBD紫外-可见吸收光谱图; (b)固体和1% (w) PMMA膜的光致发光光谱

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

表1. AOBD和POBD的物理特性

Table 1. Physical characteristics of AOBD and POBD

图4. AOBD和POBD的循环伏安曲线图

Figure 4. Cyclic voltammetry plots of AOBD and POBD

图5. AOBD和POBD的HOMO和LUMO的能级图

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

图6. CD和CPPL光谱

Figure 6. CD and CPPL spectra

图7. 器件构型和所用材料的化学结构

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

图8. AOBD和POBD器件DA (AOBD)和DP (POBD)的特性曲线: (a)电致发光光谱; (b)电流密度-电压-亮度曲线; (c)电流效率-亮度-功率效率曲线; (d) EQE-亮度曲线; (e) CPEL光谱; (f) gEL值-波长曲线

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)

表2. AOBD和POBD器件发光和效率数据

Table 2. AOBD and POBD device luminescence and efficiency data

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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

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