Synthesis of Blue-Emitting Materials with Sterically Induced Twisted Structures and Their Application in Blue Organic Light-Emitting Diode (OLED)

doi:10.6023/A25060223

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (11): 1317-1323.DOI: 10.6023/A25060223 Previous Articles Next Articles

Article

位阻诱导扭曲结构的蓝光材料合成及其在蓝色有机发光二极管(OLED)中的应用

闫安, 许世攀, 杜旭洋, 刘文平, 赵堃翔, 李胜利, 钟道昆, 周桂江^*(), 杨晓龙^*(), 孙源慧^*()

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:2025-06-17 发布日期:2025-07-09
通讯作者: 周桂江, 杨晓龙, 孙源慧
基金资助:
项目受国家自然科学基金(22375158); 项目受国家自然科学基金(22175137); 陕西省重点研发计划(2025CY-YBXM-148); 陕西省自然科学基金(2023-JC-QN-0144); 及中央高校基本科研业务费(XZY012023039)

Synthesis of Blue-Emitting Materials with Sterically Induced Twisted Structures and Their Application in Blue Organic Light-Emitting Diode (OLED)

Yan An, Xu Shipan, Du Xuyang, Liu Wenping, Zhao Kunxiang, Li Shengli, Zhong Daokun, Zhou Guijiang^*(), Yang Xiaolong^*(), Sun Yuanhui^*()

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

Received:2025-06-17 Published:2025-07-09
Contact: Zhou Guijiang, Yang Xiaolong, Sun Yuanhui
Supported by:
National Natural Science Foundation of China(22375158); National Natural Science Foundation of China(22175137); Key Research and Development Program of Shaanxi(2025CY-YBXM-148); Natural Science Foundation of Shaanxi Province(2023-JC-QN-0144); Fundamental Research Funds for the Central Universities(XZY012023039)

1. .pdf(1212KB)

Abstract

Organic light-emitting diode (OLED) technology has been widely applied in the fields of full-color flexible displays and solid-state lighting. As one of the three primary colors, blue light plays a crucial role in OLED technology, making blue-emitting materials a focal point of research in this domain. To achieve blue light emission with high color purity, blue-emitting materials need to emit light within a narrow wavelength range. However, this narrow-band emission often comes at the cost of reduced luminescence efficiency, as precise regulation of molecular energy levels to realize narrow-band emission is highly challenging in practical material design. Considering this, this work proposes an innovative molecular design strategy. Through the Suzuki-Miyaura coupling reaction of pyridine units with corresponding boronate esters, three bipyridine derivatives with different substitution sites were successfully synthesized. Subsequently, 3,6-di-tert-butylcarbazole groups were introduced to the ortho, meta, and para positions of the pyridine nitrogen atoms in the bipyridine core via C—N coupling reactions, yielding three target compounds with distinct twisted structures. In these materials, the 3,6-di-tert-butyl- carbazole unit acts as the donor and the pyridine unit as the acceptor. A significant dihedral angle exists between the carbazole substituents and the bipyridine core. This steric-induced twisted structure effectively restricts the extension of the molecular conjugated system and suppresses the energy loss due to intramolecular vibrations, thereby ensuring high color purity of blue light. Thermogravimetric analysis indicates that all three materials exhibit excellent thermal stability, with decomposition temperatures exceeding 310 ℃. Photophysical tests reveal that 2,2'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzOBPy) and 4,4'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzPBPy) show deep blue light emission at 440 nm and 422 nm, respectively, in doped films. OLED devices fabricated with these two compounds as the emissive layers have CIE coordinates of (0.152, 0.063) and (0.172, 0.098), respectively, with y values of the color coordinates both less than 0.1, indicating deep blue light emission with high color purity. Additionally, devices based on 3,3'-bis(3,6-di-tert-butyl- 9H-carbazol-9-yl)-4,4'-bipyridine (2TCzMBPy) exhibit blue-green light emission, achieving a maximum external quantum efficiency (EQE) of 3.6% and a maximum brightness of 5423 cd•m⁻².

Key words: organic light-emitting diode (OLED), twisted structure, bipyridine, blue light, high color purity

Cite this article

Yan An, Xu Shipan, Du Xuyang, Liu Wenping, Zhao Kunxiang, Li Shengli, Zhong Daokun, Zhou Guijiang, Yang Xiaolong, Sun Yuanhui. Synthesis of Blue-Emitting Materials with Sterically Induced Twisted Structures and Their Application in Blue Organic Light-Emitting Diode (OLED)[J]. Acta Chimica Sinica, 2025, 83(11): 1317-1323.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 9

Scheme 1. Synthetic routes of the three compounds

Figure 1. TGA curves of the three compounds

Compound	Absorption^a/nm	Emission^b/nm	τ^b/ns	PLQY^b/%	T_d/℃
2TCzOBPy	243, 295, 328, 342	440	2.8	50.7	337
2TCzMBPy	239, 297, 345, 391	487	11.6	94.4	317
2TCzPBPy	241, 296, 344	422	3.2	38.0	340

Table 1. Photophysical properties data of the three compounds

Figure 2. UV-Vis absorption spectra in dichloromethane solution

Figure 3. Fluorescence emission spectra in films

Figure 4. Optimized molecular structures and frontier molecular orbital distributions of the three compounds

Figure 5. Chemical structures of organic materials and simplified configuration of OLED device

Figure 6. (a) EL spectra and CIE coordinate diagram, (b) current density-voltage-luminance curves, (c) maximum external quantum efficiency-luminance curves, and (d) current efficiency-luminance-power efficiency curves based on the three materials

Device	V_on^a/V	L_max^b/(cd•m⁻²)	EQE^c/%	CE^d/(cd•A⁻¹)	PE^e/(lm•W⁻¹)	λ_EL/nm	CIE (x, y)
2TCzOBPy	4.5	2888	2.4/2.3	5.4	2.9	437	(0.172, 0.098)
2TCzMBPy	4.6	5423	3.6/2.4	11.2	6.3	496	(0.224, 0.399)
2TCzPBPy	5.4	71	0.5/—	0.3	0.2	416	(0.152, 0.063)

Table 2. Electroluminescence properties of three materials

References 33

[1]	Hua T.; Cao X.; Miao J.; Yin X.; Chen Z.; Huang Z.; Yang C. Nat. Photonics 2024, 18, 1161.
[2]	Song J.; Lee H.; Jeong E. G.; Choi K. C.; Yoo S. Adv. Mater. 2020, 32, 1907539.
[3]	Xing M.; Chen G.; Wang S.; Yin X.; Liu J.; Xue Z.; Li N.; Miao J.; Huang Z.; Yang C. Adv. Funct. Mater. 2025, 35, 2414635.
[4]	Ma J. Z.; Li Y.; Gao S.; Zhao Y.; Ding L.; Zhou D. Y.; Fan J. Acta Chim. Sinica 2025, 83, 17 (in Chinese).
	(马金珠, 李阳, 高珊, 赵越, 丁磊, 周东营, 樊健, 化学学报, 2025, 83, 17.)
[5]	Uoyama H.; Goushi K.; Shizu K.; Nomura H.; Adachi C. Nature 2012, 492, 234.
[6]	Lian M. B.; Ye Z. C.; Mu Y. X.; Hu D. H.; Liu Y.; Zhang H. L.; Ji S. M.; Huo Y. P. Chin. J. Org. Chem. 2023, 43, 573 (in Chinese).
	(连铭槟, 叶泽聪, 穆英啸, 胡德华, 刘源, 张浩力, 籍少敏, 霍延平, 有机化学, 2023, 43, 573.)
[7]	Hong G.; Gan X.; Leonhardt C.; Zhang Z.; Seibert J.; Busch J. M.; Bräse S. Adv. Mater. 2021, 33, 2005630.
[8]	Hatakeyama T.; Shiren K.; Nakajima K.; Nomura S.; Nakatsuka S.; Kinoshita K.; Ni J.; Ono Y.; Ikuta T. Adv. Mater. 2016, 28, 2777.
[9]	Qin Z. P.; Tan J. H.; Cai N.; Wang K.; Ji S. M.; Huo Y. P. Chin. J. Org. Chem. 2019, 39, 679 (in Chinese).
	(邱志鹏, 谭继华, 蔡宁, 王凯, 籍少敏, 霍延平, 有机化学, 2019, 39, 679.)
[10]	Siddiqui I.; Kumar S.; Tsai Y. F.; Gautam P.; Shahnawaz; Kesavan K.; Lin J. T.; Khai L.; Chou K. H.; Choudhury A.; Grigalevicius S.; Jou H. J. Nanomaterials 2023, 13, 2521.
[11]	Peng H.; Fan K.; Xiao L.; Hu K.; Li X. Opt. Mater. 2019, 91, 305.
[12]	Wang R. J.; Zheng F.; Liu X. L.; Wu Y. L.; Jin J. M.; Li Z. Y.; Chen W. C.; Huo Y. Chem. Commun. 2024, 60, 7946.
[13]	Sun J.; Ahn H.; Kang S.; Ko S. B.; Song D.; Um H. A.; Kim S.; Lee Y.; Jeon P.; Hwang S. H.; You Y. M.; Chu C. W. Nat. Photonics 2022, 16, 212.
[14]	Tao B.; Zheng X. K.; Wang G. L.; Sheng X. H.; Jiang H.; Li W. T.; Jin J. B.; Wang R. H.; Miao Y. Q.; Wang H.; Hang W. Y. Acta Chim. Sinica 2023, 81, 891 (in Chinese).
	(陶鹏, 郑小康, 王国良, 盛星浩, 姜贺, 李文桃, 靳继彪, 王瑞鸿, 苗艳勤, 王华, 黄维扬, 化学学报, 2023, 81, 891.)
[15]	Tan J. H.; Huo Y. P.; Cai N.; Ji S. M.; Li Z. Z.; Zhang L. Chin. J. Org. Chem. 2017, 37, 2457 (in Chinese).
	(谭继华, 霍延平, 蔡宁, 籍少敏, 李宗植, 张力, 有机化学, 2017, 37, 2457.)
[16]	Liu Z. Y.; Rao J. F.; Zhu S. J.; Wang B. Y.; Yu F.; Feng Q. Y.; Xie L. H. Acta Chim. Sinica 2023, 81, 820 (in Chinese).
	(刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海, 化学学报, 2023, 81, 820.)
[17]	Fu Y.; Liu H.; Tang B. Z.; Zhao Z. Nat. Commun. 2023, 14, 2019.
[18]	Wang B. Y.; Karikachery A. R.; Li Y.; Singh A.; Lee H. B.; Sun W.; Sharp P. R. J. Am. Chem. Soc. 2009, 131, 3150.
[19]	Shi K.; Wu C.; Zhang H.; Tong K. N.; He W.; Li W.; Jin Z.; Jung S.; Li S.; Wang X.; Gong S. L.; Zhang Y. W.; Zhang D. D.; Kang F. Y.; Chi Y.; Yang C. L. Adv. Sci. 2024, 11, 2402349.
[20]	Yang Z.; Mao Z.; Xie Z.; Zhang Y.; Liu S.; Zhao J.; Xu J.; Chi Z.; Aldred M. P. Chem. Soc. Rev. 2017, 46, 915.
[21]	Godumala M.; Choi S.; Cho M. J.; Choi D. H. J. Mater. Chem. C 2019, 7, 2172.
[22]	Wang Y. N.; Shao S. Y.; Wang L. X. Acta Chim. Sinica 2023, 81, 1202 (in Chinese).
	(王一诺, 邵世洋, 王利祥, 化学学报, 2023, 81, 1202.)
[23]	Im Y.; Kim M.; Cho Y. J.; Seo J. A.; Yook K. S.; Lee J. Y. Chem. Mater. 2017, 29, 1946.
[24]	Konidena R. K.; Lim J.; Lee J. Y. Chem. Eng. J. 2021, 416, 129097.
[25]	Chantanop N.; Saenubol A.; Itsoponpan T.; Prakanpo N.; Wongkaew P.; Loythaworn T.; Waengdongbung W.; Sudyodsuk T.; Promarak V. ChemPhotoChem 2025, 9, e202400247.
[26]	Shang Y.; Li S.; Zhang X.; Kuang C.; He Y.; Zhang X.; Wu C.; Meng Z.; Jiang X.; Meng L.; Wei G.; Meng H. Adv. Opt. Mater. 2025, 13, 2402893.
[27]	Xie M.; Ma C.; Zhou Y.; Song J.; Zhang L.; Zhang S.-T.; Sun Q.; Yang W.; Xue S. Adv. Funct. Mater. 2025, 35, 2422822.
[28]	Wei W.; Li J.; Liu D.; Mei Y.; Lan Y.; Tian H.; Niu R.; Liu B. New J. Chem. 2021, 45, 16732.
[29]	Jung S. H.; Park S. H.; Kwon N. Y.; Park J. Y.; Kang M. J.; Koh C. W.; Cho M. J.; Park S.; Choi D. H. ACS Appl. Mater. Interfaces 2023, 15, 56106.
[30]	Guo R.; Ye S.; Wang Y.; Duan Y.; Di K.; Wang L. J. Mater. Chem. C 2021, 9, 13392.
[31]	Yang G.-X.; Chen Y.; Zhu J.-J.; Song J.-Y.; Tang S.-S.; Ma D.; Tong Q.-X. Dyes Pigm. 2021, 187, 109088.
[32]	Wang T.; Huang Z.; Zhang H.; Miao J.; Yang C. Adv. Funct. Mater. 2024, 34, 2408119.
[33]	Zhu Y.; Zeng S.; Gong W.; Chen X.; Xiao C.; Ma H.; Zhu W.; Yeob Lee J.; Wang Y. Chem. Eng. J. 2022, 450, 138459.

位阻诱导扭曲结构的蓝光材料合成及其在蓝色有机发光二极管(OLED)中的应用

Synthesis of Blue-Emitting Materials with Sterically Induced Twisted Structures and Their Application in Blue Organic Light-Emitting Diode (OLED)

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 9

References 33

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Li Yuan, Liu Wenna, Zheng Xingwang. Investigation into Electrogenerated Chemiluminescence Behavior of Tris(bipyridine)ruthenium(II)/silica Nanoparticles Electrocatalyzed by Cu(tris(hydroxymethyl)aminomethane)₄²⁺ Complex [J]. Acta Chim. Sinica, 2015, 73(7): 749-754.
[2]	BU Zhan-Wei, WANG Zhi-Qiang, QIN Gang, CUI Yuan-Chen, CAO Shao-Kui. A Mechanistic Study for Cyclic Carbonate Formation from CO₂ and Epoxides Catalyzed by Ruthenium 2,2 -Bipyridine Complex [J]. Acta Chimica Sinica, 2010, 68(18): 1871-1875.
[3]	PI, Ya-Juan ^a TANG, Hao ^b ZHAO, Guo-Sheng ^c SUN, Run-Guang ^b ZHU, Wei-Hong ^*,a. Synthesis and Electroluminescent Properties of Red Dopant with High Color Purity [J]. Acta Chimica Sinica, 2008, 66(12): 1460-1464.
[4]	CHEN Xiao-Tong; DONG Bin; CUI Meng-Chao; WANG Ke-Zhi*; JIN Lin-Pei. A Comparative Study on Electrochemiluminescent Properties of a Series of Ruthenium(II) Complexes [J]. Acta Chimica Sinica, 2007, 65(12): 1181-1184.
[5]	CAO Xiang-Qian; CHEN Jin-Xiang; CHEN Yang; LI Hong-Xi; REN Zhi-Gang; ZHANG Yong; LANG Jian-Ping*^,1,2. Synthesis, Crystal Structure and Properties of a 3D Porous Coordination Polymer {[Zn₂(mal)₂(4,4'-bipy)(H₂O)₂]• 2(H₂O)_0.25}_∞ (mal＝malonate) [J]. Acta Chimica Sinica, 2006, 64(24): 2496-2500.
[6]	TAO Ying; LI Mei-Jin; ZHANG Li-Yan^1,3; CHEN Xi*^{,1,2. Effects of Metal Ions on the Electrochemiluminescence of Ru(bpy)₃^2＋ [J]. Acta Chimica Sinica, 2006, 64(18): 1885-1888.}
[7]	TAO Long-Ling, XUE Sai-Feng², ZHU Qian-Jiang², TAO Zhu², YU Yi-Hua*^,1. 2D NMR Studies on the Interaction of Symmetrical Tetramethylcucurbit[6]uril with 5,5'-Bimethyl-2,2'-bipyridine [J]. Acta Chimica Sinica, 2006, 64(14): 1474-1478.
[8]	LI Hong-Yang, SHI Feng, PENG Xiao-Jun, ZHANG Rong, CHEN Xiao-Qiang, ZHANG Li-Zhu, SUN Li-Cheng. Properties of a Dinuclear Mn(Ⅲ,Ⅲ) Complex with a Tri-phenolate Ligand [N₄O₃]^3- and a New Complex Containing a Ligand Covalently Linked to Ruthenium Tris-bipyridine [J]. Acta Chimica Sinica, 2004, 62(9): 916-922.
[9]	Fu Xiaogang;Wu Lizhu;Zhang Liping;Tong Zhenhe. Photosensitized Oxidation of Alkenes with Nafion-Loaded [Ru(bpy)_3] ~(2+) as Photosensitizer [J]. Acta Chimica Sinica, 2003, 61(7): 1036-1039.
[10]	Yin Fuling;Shen Jia;Zou Jiajia;Li Rongchang. Study on the Synthesis, Characterization, Crystal Structure and Anticancer Acitivity of a Bridging Ligand Complex of Cu(II) with 2,2'- Bipyridine and Demethylcantharate [J]. Acta Chimica Sinica, 2003, 61(4): 556-561.
[11]	Gao Enjun;Zhang Dan;Liu Qitao. Studies on the Crystal Structure and Stability in Solution of Mixed Ligand Complex of Palladium (II) with 2,2'-Bipyridine and L-Aspartic Acid [J]. Acta Chimica Sinica, 2003, 61(11): 1834-1838.
[12]	Chen Xi;Yi Changqing;Li Meijin;Li Zhen;Wang Xiaoru. Effect of Substituents of Amines on Electrochemiluminescence of Tri (2,2'-bipyridine)ruthenium with Some Amines [J]. Acta Chimica Sinica, 2002, 60(9): 1662-1667.
[13]	Li Dan;Qi Zhiyu;Feng Qiao;Li Rongzhen;Feng Xiaolong;Cai Jiwen. Syntheses, Crystal Structures and Photoluminescence of [Au_2(PPh_3) _2(μ-4,4'-bpy)](ClO_4)_2 and [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4'-bpy)] (BF_4)_2 Complexes [J]. Acta Chimica Sinica, 2002, 60(9): 1637-1643.
[14]	Li Feng;Lin Xiangqin;Cui Hua. Two electrochemiluminescence pathways of Ru(bpy)^2^+~3/C2O^2^-~4 system on platinum electrode [J]. Acta Chimica Sinica, 2002, 60(2): 281-286.
[15]	Feng Qiao;Li Dan;Yin Yegao;Feng Xiaolong;Cai Jiwen. Synthesis, Structure and Spectroanalysis Studies of a Five- coordinated Cu(I) Complex [Cu(4'-Phtpy)(PPh_3)_2](BF_4) [J]. Acta Chimica Sinica, 2002, 60(12): 2167-2171.