Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3,6-Diphenylselenylcarbazole

doi:10.6023/A25090323

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (2): 248-256.DOI: 10.6023/A25090323 Previous Articles Next Articles

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基于3,6-二苯硒基咔唑的多重共振热活化延迟荧光分子

汪庆辉^a^,^†(), 任正^a^,^†(), 张凯^b^,^*(), 周东营^a^,^*(), 樊健^a^,^c^,^*()

^a 苏州大学功能纳米与软物质研究院仿生界面材料科学全国重点实验室苏州 215123
^b 曲阜师范大学物理与工程学院物理与工程学院山东曲阜 273165
^c 中国科学院福建物质结构研究所结构化学国家重点实验室结构化学国家重点实验室福建福州 350002

投稿日期:2025-09-27 发布日期:2025-11-10
基金资助:
项目受国家重点研发计划(2020YFA0714604); 项目受国家重点研发计划(2024YFB3612102); 江苏省国际科技合作/港澳台科技合作项目(BZ2023053)

Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3,6-Diphenylselenylcarbazole

Qinghui Wang^a(), Zheng Ren^a(), Kai Zhang^b^,^*(), Dongying Zhou^a^,^*(), Jian Fan^a^,^c^,^*()

^a State Key Laboratory of Bioinspired Interfacial Materials Science, Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China
^b College of Physics and Engineering, Qufu Normal University, Qufu 273165, Shandong, China
^c State Key Laboratory of Structural Chemistry, Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China

Received:2025-09-27 Published:2025-11-10
Contact: *E-mail: 15692312996@163.com;dyzhou@suda.edu.cn;jianfan@suda.edu.cn
About author:
†These authors contributed equally to this work.
Supported by:
National Key R&D Program of China(2020YFA0714604); National Key R&D Program of China(2024YFB3612102); International Science and Technology Innovation Cooperation/Hong Kong, Macao and Taiwan Science and Technology Innovation Cooperation Project of Jiangsu Province, China(BZ2023053)

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Abstract

Abstract Conventional multiple resonance thermally activated delayed fluorescence material (MR-TADF) has a narrow emission spectrum with full width at half maximum (FWHM) <30 nm due to its planar rigid structure that suppresses vibrational relaxation and thus makes devices with higher color purity, but it usually faces the problem of a low rate of reverse intersystem crossing (k_RISC), and the device has a significant roll-off in efficiency at high luminance. Therefore, a molecule 2SetCzBN was designed and synthesized by introducing selenium atoms into the 3, 6 position of carbazole, which utilizes the heavy-atom effect of selenium to enhance the spin-orbit coupling effect of S₁ and T₁, accelerating the reverse intersystem crossing rate and thus decreasing the efficiency roll-off of the device at high luminance. The thermal decomposition temperature (temperature at 5% mass loss, T_d) of the compound 2SetCzBN was 388 ℃, proving that it can be sufficient to withstand the heat treatment procedures during device preparation. The FWHM of 2SetCzBN in dilute toluene solution is 26 nm and the ΔE_ST is only 0.14 eV. The prompt fluorescence lifetimes of 2SetCzBN film is 1.3 ns and the delayed fluorescence lifetime is 3.27 μs. The orbital distribution and geometric configuration of 2setczbn are simulated, and the molecule has a high oscillator strength (f) of 0.4577. Meanwhile, the S₁ and T₁ of 2SetCzBN are hybrid local charge transfer (HLCT) excited states, and the T₂ energy level is mainly local excited states (LE). In addition, due to the influence of heavy atom effect, 2SetCzBN has a large spin-orbit coupling constant of 2.132 cm⁻¹, and finally achieves a high reverse intersystem crossing rate (2.49×10⁶ s⁻¹). Remarkably, when 2SetCzBN was doped in the host material PhCzBCz with 15% (w) Firpic as the sensitizer, the organic light-emitting diode (OLED) device achieves a maximum EQE of 27.6%, and 22.2% at 10³ cd/m². Furthermore, the maximum EQE can reach 31.3% with the optimal thickness of the electron-transport layer (50 nm).

Key words: thermally activated delayed fluorescence, heavy atom effect, multiple resonance effect, selenium, organic light-emitting diode

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Qinghui Wang, Zheng Ren, Kai Zhang, Dongying Zhou, Jian Fan. Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3,6-Diphenylselenylcarbazole[J]. Acta Chimica Sinica, 2026, 84(2): 248-256.

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Fig. & Tab. 11

Scheme 1. Synthetic route of 2SetCzBN

Figure 1. (a) The energy and distribution of HOMO and LUMO of 2SetCzBN molecules in solvents. (b) The adiabatic excitation energy and spin orbit coupling constant (SOC) of the excited state. (c) The transition properties of singlet and triplet states (The right side of the arrow indicates the proportion of LE)

Figure 2. (a) UV/vis absorption, fluorescence (298 K), and phosphorescence (77 K) spectra of 2SetCzBN in toluene (10−5 mol/L). (b) Transient photoluminescence (PL) decay curve for the 2SetCzBN in film via vacuum processes at 300 K

化合物	T_d^a/^°C	HOMO^b/eV	LUMO^b/eV	E_g^c/eV
2SetCzBN	388	－5.33	－2.79	2.54

Table 1. Thermodynamic and electrochemical data of 2SetCzBN

化合物	λ_abs^a/nm	λ_em^a/nm	FWHM^a/nm	S₁^b/eV	T₁^b/eV	ΔE_ST^c/eV
2SetCzBN	474	496	26	2.61	2.47	0.14

Table 2. Summary of the photophysical properties of 2SetCzBN

化合物	Ф_PL/%	Ф_d/%	τ_p/ns	τ_d/μs	K_p/10⁸ s⁻¹	K_d/10⁵ s⁻¹	K_r^S/10⁷ s⁻¹		K_IC/10⁷ s⁻¹	K_ISC/10⁸ s⁻¹	K_RISC/10⁶ s⁻¹
2SetCzBN	70	63.98	1.30	3.27	7.69	2.14		4.63	1.98	7.03	2.49

Table 3. Kinetic parameters of 2SetCzBN

Figure 3. EL performance of 2SetCzBN based binary OLED. (a) Normalized EL spectra curves of the 2SetCzBN. (b) Current density-voltage characteristics of 2SetCzBN. (c) Current efficiency (CE)-luminance characteristics of the 2SetCzBN. (d) External quantum efficiency (EQE)-luminance characteristics of the 2SetCzBN

发光材料	Dop (w/%)	V_on^a/V	EQE^b/%		CE_max^c/(cd•A⁻¹)		λ_em/nm	FWHM/nm
发光材料	Dop (w/%)	V_on^a/V	Max	@10³ cd/m²	CE_max^c/(cd•A⁻¹)		λ_em/nm	FWHM/nm
2SetCzBN	1 2 5 10	3.2 3.2 3.1 3.1	25.4 27.5 27.7 25.9	9.8 11.7 13.9 15.2	60 70 80 85	500 500 504 508		32 32 36 44

Table 4. EL performance of 2SetCzBN based binary OLED

发光材料	Dop (w/%)	V_on/V		EQE/%			CE/(cd•A⁻¹)		λ_em/nm	FWHM/nm
发光材料	Dop (w/%)	V_on/V		Max	@10³ cd/m²		Max	@10³ cd/m²	λ_em/nm	FWHM/nm
2SetCzBN 2SetCzBN:Firpic	2 2		3.2 3.1	27.5 27.6	11.7 22.2		70.0 70.0	29.7 56.2	500 500	32 32

Table 5. EL performance of 2SetCzBN based ternary TSF-OLED and binary OLED

Figure 4. EL performance of 2SetCzBN based ternary TSF-OLED and binary OLED with doping concentrations of 2% (w). (a) Normalized EL spectra curves of the 2SetCzBN. (b) Current density-voltage characteristics of 2SetCzBN. (c) Current efficiency (CE)-luminance characteristics of the 2SetCzBN. (d) External quantum efficiency (EQE)-luminance characteristics of the 2SetCzBN

Figure 5. EL performance of 2SetCzBN based ternary TSF-OLED at different ETL thicknesses with doping concentrations of 2% (w). (a) Normalized EL spectra curves of the 2SetCzBN. (b) Current density-voltage characteristics of 2SetCzBN. (c) Current efficiency (CE)-luminance characteristics of the 2SetCzBN. (d) External quantum efficiency (EQE)-luminance characteristics of the 2SetCzBN

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基于3,6-二苯硒基咔唑的多重共振热活化延迟荧光分子

Multiple Resonance Thermally Activated Delayed Fluorescence Molecule Based on 3,6-Diphenylselenylcarbazole

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