Synthesis and Electroluminescence Performance of Thermally Activated Delayed Fluorescence Materials Based on 4-Cyanopyrimidine Acceptor

doi:10.6023/A26030070

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (7): 1040-1048.DOI: 10.6023/A26030070 Previous Articles Next Articles

Article

基于4-氰基嘧啶受体的热活化延迟荧光材料合成及其电致发光性能研究

陶骏飞, 许世攀, 杜旭洋, 尹赫, 闫安, 杭怀腾, 陈亮, 周桂江^*(), 孙源慧^*(), 杨晓龙^*()

西安交通大学化学学院储能材料与器件教育部工程研究中心西安市新能源材料化学重点实验室西安 710049

投稿日期:2026-03-08 发布日期:2026-04-29
基金资助:
国家自然科学基金(22375158); 陕西省重点研发计划(2025CY-YBXM-148); 中央高校基本科研业务费(xtr052025015); 中央高校基本科研业务费(xtr072024032)

Synthesis and Electroluminescence Performance of Thermally Activated Delayed Fluorescence Materials Based on 4-Cyanopyrimidine Acceptor

Junfei Tao, Shipan Xu, Xuyang Du, He Yin, An Yan, Huaiteng Hang, Liang Chen, Guijiang Zhou^*(), Yuanhui Sun^*(), Xiaolong Yang^*()

Xi'an Key Laboratory of Chemistry for New Energy Materials, Engineering Research Center of Energy Storage Materials and Devices (Ministry of Education), School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, China

Received:2026-03-08 Published:2026-04-29
Contact: * E-mail: zhougj@xjtu.edu.cn; sunyuanhui@xjtu.edu.cn; xiaolongyang@xjtu.edu.cn
Supported by:
National Natural Science Foundation of China(22375158); Key Research and Development Program of Shaanxi(2025CY-YBXM-148); Fundamental Research Funds for the Central Universities(xtr052025015); Fundamental Research Funds for the Central Universities(xtr072024032)

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Abstract

Organic light-emitting diodes (OLEDs) have advantages such as low driving voltage, high brightness, high color purity, flexible display capabilities, lightweight construction, and fast response times, which position them as promising next-generation display materials. Thermally activated delayed fluorescence (TADF) materials can achieve 100% exciton utilization through the reverse intersystem crossing (RICS) process and are known as the third-generation luminescent materials. TADF molecules achieve a small singlet-triplet energy gap (ΔE_ST) by separating the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) through a donor-acceptor (D-A) twisted structure, thereby enhancing the RISC rate. Currently, many donor molecules have been developed, while acceptor molecules have not been fully explored. In this study, 4-cyanopyrimidine was used as the acceptor, and phenoxazine, diphenylamine, carbazole, and acridine were used as donors. The donors and acceptors were connected through a benzene ring bridge by the Suzuki- Miyaura and Buchwald-Hartwig coupling reactions, and four D-A type TADF materials, PhPX-CN, PhDPA-CN, PhCz-CN, and PhAd-CN, were synthesized. The four prepared TADF molecules all have a twisted D-A structure, with the HOMO and LUMO located on the donor and acceptor fragments, respectively, achieving spatial separation of HOMO and LUMO. Therefore, the four TADF molecules exhibit small singlet-triplet energy gaps (<0.3 eV). As the electron-donating ability of the donors decreases in sequence, the maximum emission spectra of the fluorescent materials PhPX-CN, PhAd-CN, PhDPA-CN, and PhCz-CN gradually blue-shift from 513 nm to 502, 496, and 440 nm. When PhDPA-CN and PhCz-CN were respectively used as guest materials and doped in the host materials 4,4′-di(N-carbazolyl)-1,1′-biphenyl (CBP) and 1,3-bis(carbazol-9-yl) benzene (mCP), the maximum external quantum efficiencies (EQE) of the OLED devices are 6.85% and 3.04%, respectively, achieving green and blue emissions. 4-Cyanopyrimidine has excellent electron-withdrawing ability and can be used to prepare TADF materials with common donor molecules. Moreover, the emission wavelength can be precisely controlled by changing the electron-donating ability of the donors.

Key words: 4-cyanopyrimidine acceptor, donor-acceptor (D-A) structure, energy level regulation, thermally activated delayed fluorescence (TADF), organic light-emitting diodes (OLEDs)

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Junfei Tao, Shipan Xu, Xuyang Du, He Yin, An Yan, Huaiteng Hang, Liang Chen, Guijiang Zhou, Yuanhui Sun, Xiaolong Yang. Synthesis and Electroluminescence Performance of Thermally Activated Delayed Fluorescence Materials Based on 4-Cyanopyrimidine Acceptor[J]. Acta Chimica Sinica, 2026, 84(7): 1040-1048.

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Fig. & Tab. 12

Scheme 1. Syntheses of PhAd-CN、PhCz-CN、PhPX-CN and PhDPA-CN

Figure 1. TGA Curve Graph

Figure 2. Ultraviolet-visible absorption spectra and fluorescence emission spectra at room temperature in toluene solution

Compound	λ_abs^a/nm	λ_PL solution ^b/film ^c (nm)	FWHM solution ^b/film ^c (nm)	τ_PF^d/τ_DF^e (ns/μs)	E_HOMO^f/E_LUMO^g (eV)	E_g^h/eV	PLQYⁱ/%
PhPX-CN	284, 324, 396	513/518	89/91	8.11/9.50	－5.22/－2.98	2.24	67
PhAd-CN	385	502/522	80/90	29.52/9.11	－5.05/－2.78	2.28	52
PhDPA-CN	294, 376	496/510	83/85	14.01/10.95	－5.30/－2.97	2.33	59
PhCz-CN	288, 356	440/470	75/94	19.74/9.60	－5.66/－2.98	2.68	45

Table 1. Summary of optical properties

Figure 3. Emission spectra doped in CBP films at a concentration of 15% (w)

Figure 4. Transient PL decay curve of 15% (w) doped CBP film

Figure 5. Cyclic voltammetry graph

Figure 6. The four TADF molecules based on the optimized S0 geometric configuration, the distribution of HOMO/LUMO, energy levels, energy gaps, and the energy level diagram of S1/T1

Figure 7. The NTO distribution map of S0→S1 based on the optimized S1 configuration and the S0 geometry showing the twisting angle between donor and acceptor

Figure 8. Molecular structural formulas and energy level diagrams of device structures and functional layer materials

Figure 9. (a) EL spectra, (b) current density-voltage-luminance curves, (c) EQE-L curves of devices and (d) current efficiency-luminance characteristics, and power efficiency-luminance characteristics of A3 and B3

Device	V_on^a/V	L_max^b/ (cd•m⁻²)	EQE_max^c/%	CE_max^d/ (cd•A⁻¹)	PE_max^e/ (lm•W⁻¹)	λ_EL^f/ nm	FWHM/nm
A1	5.5	1106	6.52	18.03	9.44	500	84
A2	5.0	1253	6.85	19.85	11.34	508	86
A3	5.0	1503	6.83	20.13	11.50	512	87
B1	7.0	340	1.14	1.32	0.59	464	96
B2	6.0	426	1.72	2.11	1.11	468	85
B3	6.0	712	3.04	6.26	3.27	476	112

Table 2. Electroluminescent performance of devices based on PhDPA-CN and PhCz-CN

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基于4-氰基嘧啶受体的热活化延迟荧光材料合成及其电致发光性能研究

Synthesis and Electroluminescence Performance of Thermally Activated Delayed Fluorescence Materials Based on 4-Cyanopyrimidine Acceptor

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