一种三氰基取代的9-苯基芴化合物的合成及其激基复合物发光

doi:10.6023/cjoc202401024

有机化学 ›› 2024, Vol. 44 ›› Issue (8): 2595-2602.DOI: 10.6023/cjoc202401024 上一篇下一篇

研究论文

一种三氰基取代的9-苯基芴化合物的合成及其激基复合物发光

曹洪涛^a, 曹庆^a, 胡杨军^a, 余梓萌^a, 解鑫淼^a, 常永正^a^,^*(), 侯鹏飞^a^,^*(), 汪莎莎^a, 解令海^a^,^b^,^*()

a 南京邮电大学材料科学与工程学院/化学与生命科学学院有机电子与信息显示国家重点实验室南京 210023
b 河南大学柔性电子学院/河南省柔性电子产业技术研究院郑州 450046

收稿日期:2024-01-18 修回日期:2024-03-24 发布日期:2024-04-24
基金资助:
国家自然科学基金(62288102); 国家自然科学基金(22275098); 中国博士后科学基金面上项目(2022M711684); 国家留学基金(202008320051); 江苏省高等学校基础科学(自然科学)研究面上项目(22KJB430036); 及南京邮电大学校级自然科学基金(NY221084); 及南京邮电大学校级自然科学基金(NY221085); 及南京邮电大学校级自然科学基金(NY222157)

Synthesis and Exciplex Emission of a Tricyano-substituted 9-Phenylfluorene Compound

Hongtao Cao^a, Qing Cao^a, Yangjun Hu^a, Zimeng Yu^a, Xinmiao Xie^a, Yongzheng Chang^a(), Pengfei Hou^a(), Shasha Wang^a, Linghai Xie^a^,^b()

a State Key Laboratory of Organic Electronics and Information Displays, College of Materials Science and Engineering, College of Chemistry and Life Sciences, Nanjing University of Posts & Telecommunications, Nanjing 210023
b School of Flexible Electronics and Henan Institute of Flexible Electronics, Henan University, Zhengzhou 450046

Received:2024-01-18 Revised:2024-03-24 Published:2024-04-24
Contact: *E-mail: iamyzchang@njupt.edu.cn; 52274300048@stu.ecnu.edu.cn; iamlhxie@njupt.edu.cn
Supported by:
National Natural Science Foundation of China(62288102); National Natural Science Foundation of China(22275098); China Postdoctoral Science Foundation(2022M711684); State Scholarship Fund of China Scholarship Council(202008320051); Natural Science Foundation of the Jiangsu Higher Education Institutions(22KJB430036); Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY221084); Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY221085); Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY222157)

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摘要/Abstract

激基复合物发光材料因易实现小的单重态-三重态能隙差, 更有利于实现高效热活化延迟荧光发射(TADF)而受到广泛关注. 然而, 激基复合物发光在简易式设计开发电子受体分子方面仍面临一些挑战. 通过非对称修饰的三氰基取代, 设计合成出了一种9-苯基芴型电子受体分子9-[6-(2-氰基-7-异氰基-9-苯基-9H-芴-9-基)-9-乙基-9H-咔唑-3-基]-9-苯基-9H-芴-2,7-二腈(TriCNDPFCz). 经过与传统的电子给体分子1,1-双[(二-4-甲苯氨基)苯基]环己烷(TAPC)掺杂, 实现了高效的激基复合物发光, 对应的最大电流效率为46.7 cd•A^－1, 功率效率为52.3 lm•W^－1, 外量子效率为14.5%. 实验结果表明, 在9-苯基芴骨架上进行非对称的三氰基取代, 能够促使分子具有强吸电子的能力, 进而有利于构筑优良的电子受体材料和激基复合物发光.

关键词: 9-苯基芴, 氰基取代, 非对称修饰, 激基复合物

Exciplex-emitters are attractive due to their distinct feature of easily achieving small singlet-triplet energy splitting for thermally activated delayed fluorescence (TADF), but face with challenges in convenient design of electron acceptors. New 9-phenylfluorene-based acceptor 9-[6-(2-cyano-7-isocyano-9-phenyl-9H-fluoren-9-yl)-9-ethyl-9H-carbazol-3-yl]-9-phenyl- 9H-fluorene-2,7-dicarbonitrile (TriCNDPFCz) was designed and synthesized through tricyano-substitution. By mixing TriCNDPFCz with conventional donor 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), bright exciplex-TADF was obtained with a maximum current efficiency of 46.7 cd•A^－1, power efficiency of 52.3 lm•W^－1 and external quantum efficiency of 14.5%. The experimental characterizations indicate that tricyano-substitution in 9-phenylfluorene skeleton can form strong electron-accepting ability, which is useful and convenient for constructing electron acceptor in exciplex emission.

Key words: 9-phenylfluorene, cyano-substitution, asymmetric modification, exciplex emission

引用此文

曹洪涛, 曹庆, 胡杨军, 余梓萌, 解鑫淼, 常永正, 侯鹏飞, 汪莎莎, 解令海. 一种三氰基取代的9-苯基芴化合物的合成及其激基复合物发光[J]. 有机化学, 2024, 44(8): 2595-2602.

Hongtao Cao, Qing Cao, Yangjun Hu, Zimeng Yu, Xinmiao Xie, Yongzheng Chang, Pengfei Hou, Shasha Wang, Linghai Xie. Synthesis and Exciplex Emission of a Tricyano-substituted 9-Phenylfluorene Compound[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2595-2602.

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图/表 7

Scheme 1. Molecular design strategy in this work

Scheme 2. Synthetic routes of compound TriCNDPFCz Reagents and conditions: (a) 2-bromo-9-phenyl-9H-fluorene-9-ol, BF3? OEt2, CH2Cl2, 30 ℃, 5 h; (b) K4Fe(CN)6?3H2O, Pd(dppf)Cl2, Na2CO3, TBAB, DMF, 150 ℃, 24 h

Figure 1. Chemical structures of (a) TAPC, and (b) UV-Vis ab- sorption and (c) PL spectra of TAPC, TriCNDPFCz and TAPC: TriCNDPFCz in the film-state

Figure 2. (a) Fluorescence decays of TAPC (excitation: 335 nm, detection: 388 nm) and TriCNDPFCz (excitation: 375 nm, detection: 463 nm) and (b) fluorescence decay of TAPC:TriCNDPFCz (excitation: 375 nm, detection: 535 nm) in film-state at 300 K, (c) temperature-dependent transient fluorescence decays of TAPC:TriCNDPFCz (excitation: 375 nm, detection: 535 nm) in film-state and (d) fluorescence (excitation: 350 nm) and phosphorescence (excitation: 350 nm) spectra of TAPC:TCNDPFCz in film-state at 77 K

Emitter	λ_PL,max^a/nm	Φ_p^a/%	S₁^b/eV	T₁^b/eV	ΔE_ST/eV	Decay time^a
Emitter	λ_PL,max^a/nm	Φ_p^a/%	S₁^b/eV	T₁^b/eV	ΔE_ST/eV	τ/ns	χ²
TAPC	388	12	4.05	3.11	0.94	0.9 (45%), 4.0 (55%)	0.959
TriCNDPFCz	463	22	3.15	2.51	0.64	35.7 (100%)	0.984
TAPC:TriCNDPFCz	535	59	2.63	2.60	0.03	42.0 (40%), 230.9 (60%)	0.998

Table 1. Photophysical properties of the deposited films of TAPC, TriCNDPFCz and TAPC:TriCNDPFCz

Figure 3. (a) General structure, (b) EL spectra at 10 V, (c) current density-voltage-luminance and (d) current efficiency-luminance-power efficiency characteristics of device I

Device	V_turn-on^a/V	L_max^b/(cd•m^-2)	η_c^b^,^c/(cd•A^-1)	η_p^b^,^c/(lm•W^-1)	η_p^b^,^c/%	λ_El^d/nm	CIE^d
I	2.5	20363	46.7, 33.5	52.3, 32.1	14.5, 10.4	544	(0.41, 0.55)

Table 2. Summary of electroluminescence performance for device I

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一种三氰基取代的9-苯基芴化合物的合成及其激基复合物发光

Synthesis and Exciplex Emission of a Tricyano-substituted 9-Phenylfluorene Compound

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