Coordination Fragment Modulation and Electroluminescent Performance of Benzimidazole-based Tetradentate Cyclometalated Platinum(II) Complexes

doi:10.6023/A26050148

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (8): 1236-1242.DOI: 10.6023/A26050148 Previous Articles Next Articles

Article

苯并咪唑基四齿环金属铂(II)配合物的配位片段调控及其电致发光性能

黄宏^a, 邓德朋^a^,^b, 卢丹^a^,^b, 申月^a^,^*(), 李能泉^a^,^*(), 张友明^a, 华涛^a, 任保轶^b

^a 深圳信息职业技术大学未来产业技术研究院(科技仪器应用工程学院) 未来产业技术研究院(科技仪器应用工程学院) 深圳 518172
^b 沈阳化工大学理学院理学院沈阳 110142

投稿日期:2026-05-06 发布日期:2026-06-30
通讯作者: 申月, 李能泉
基金资助:
深圳市科技计划项目(20231127123500001); 深圳市科技计划项目(JCYJ20240813143022029); 深圳信息职业技术大学项目(TD2024E002); 深圳信息职业技术大学项目(SZIIT2025KJ045); 深圳信息职业技术大学项目(SZIIT2024KJ021); 深圳信息职业技术大学项目(SZIIT2025KJ063); 广东省普通高等高校创新团队项目(TD2025C005); 辽宁省科技计划联合计划(科技攻关重点项目)(2024JH2/102600226)

Coordination Fragment Modulation and Electroluminescent Performance of Benzimidazole-based Tetradentate Cyclometalated Platinum(II) Complexes

Hong Huang^a, Depeng Deng^a^,^b, Dan Lu^a^,^b, Yue Shen^a^,^*(), Nengquan Li^a^,^*(), Youming Zhang^a, Tao Hua^a, Bao-Yi Ren^b

^a School of Engineering and Technology Instrument Application Engineering, Institute of Technology for Future Industry, Shenzhen University of Information Technology, Shenzhen 518172, China
^b College of Science, Shenyang University of Chemical Technology, Shenyang 110142, China

Received:2026-05-06 Published:2026-06-30
Contact: Yue Shen, Nengquan Li
Supported by:
Shenzhen Science and Technology Program(20231127123500001); Shenzhen Science and Technology Program(JCYJ20240813143022029); Shenzhen University of Information Technology(TD2024E002); Shenzhen University of Information Technology(SZIIT2025KJ045); Shenzhen University of Information Technology(SZIIT2024KJ021); Shenzhen University of Information Technology(SZIIT2025KJ063); Guangdong Provincial University Innovation Team Project(TD2025C005); Liaoning Province Science and Technology Plan Joint Plan(Technology Tackling Key Problems Plan Project)(2024JH2/102600226)

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Abstract

Cyclometalated platinum(II) complexes serve as core guest materials for high-performance phosphorescent organic light-emitting diodes (OLEDs) due to their excellent exciton utilization efficiency and structural modifiability. In this work, rigid 5H-benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (BZI) was adopted as the fundamental building block. Two tetradentate cyclometalated platinum(II) complexes, namely Pt-py and Pt-bt, were rationally designed and synthesized by introducing pyridine and benzothiazole moieties, respectively. Both complexes exhibit outstanding thermodynamic and electrochemical stabilities. Theoretical simulation, photophysical measurements and electroluminescent device results reveal that Pt-py possesses a highly rigid molecular skeleton and weak excited-state geometric distortion, which effectively suppresses non-radiative decay. It exhibits high photoluminescence quantum yield and radiative decay rate, as well as excellent carrier trapping capability, enabling efficient charge recombination and sufficient host-guest energy transfer in the emitting layer. The corresponding doped OLED exhibit outstanding electroluminescent properties and extremely low efficiency roll-off, with a maximum luminance of 65782 cd•m⁻², current efficiency of 83.3 cd•A⁻¹, power efficiency of 86.5 lm•W⁻¹ and external quantum efficiency (EQE) of 23.4%. Its efficiency roll-off is only 4.7% at a practical luminance of 1000 cd•m⁻². In contrast, Pt-bt with an extended conjugated plane achieves obvious emission redshift and realizes orange-red phosphorescence. However, the enlarged conjugated structure aggravates excited-state structural distortion and weakens carrier trapping ability, resulting in incomplete host-to-guest energy transfer and severe exciton quenching. Restricted by the energy gap law, the resultant device shows mediocre electroluminescence performance, with a low maximum EQE of 10.4% and serious efficiency roll-off. These results indicate that the rigid BZI moiety provides a structural basis for the efficient phosphorescence emission of Pt(II) complexes. Rational selection of coordinated fragments enables the regulation of emission color, efficiency and device stability. This work offers insights for the molecular design of novel tetradentate Pt(II)-based phosphorescent materials and their applications in OLEDs.

Key words: cyclometalated platinum(II) complexes, electroluminescence, benzimidazole, pyridine, benzothiazole

Cite this article

Hong Huang, Depeng Deng, Dan Lu, Yue Shen, Nengquan Li, Youming Zhang, Tao Hua, Bao-Yi Ren. Coordination Fragment Modulation and Electroluminescent Performance of Benzimidazole-based Tetradentate Cyclometalated Platinum(II) Complexes[J]. Acta Chimica Sinica, 2026, 84(8): 1236-1242.

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Fig. & Tab. 8

Figure 1. Chemical structures of the complexes Pt-py and Pt-bt

Figure 2. (a) Front and side views of the molecular structures in the ground states, (b) geometric comparison of S0, S1 and T1 and RMSD values, (c) distribution of frontier orbitals and energy and (d) natural transition orbitals of the T1→S0 state of the complexes Pt-py and Pt-bt

Figure 3. Normalized UV-Vis absorption spectra and photoluminescence spectra of the complexes Pt-py and Pt-bt in dichloromethane

Complex	λ_abs^a/nm	λ_em^a/nm	Eopt g^b/eV	τ^c/µs	Ф^c/%	HOMO^d/eV	HOMO^e/eV	T_d/℃
Pt-py	386	531	2.63	3.31	99.02	-5.29	-2.66	445.44
Pt-bt	409	606	2.44	5.69	57.24	-5.35	-2.91	389.51

Table 1. Photophysical, electrochemical and thermodynamic properties of the complexes Pt-py and Pt-bt

Figure 4. Transient spectra of the complexes Pt-py and Pt-bt in DMIC-TRZ films with a doping concentration of 5%

Figure 5. Cyclic voltammograms of the complexes Pt-py and Pt-bt

Figure 6. EL performance of doped OLEDs based on Pt-py and Pt-bt. (a) Normalized EL spectra; (b) Current density-voltage-luminance curves; (c) External quantum efficiency-luminance curves; (d) Current efficiency-luminance-power efficiency curves

Complex	λ_EL^a/nm	L_max/(cd•m⁻²)	V_on/V	CE_max/(cd•A⁻¹)	PE_max/(lm•W⁻¹)	EQE_max/500/1000/%	CIE1931 coordinates^b
Pt-py	523	65782	2.8	83.3	86.5	23.4/23.3/22.3	(0.35, 0.61)
Pt-bt	582	19232	2.8	24.8	27.8	10.4/6.6/5.6	(0.46, 0.44)

Table 2. EL performance of Pt-py and Pt-bt based doped OLEDs

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苯并咪唑基四齿环金属铂(II)配合物的配位片段调控及其电致发光性能

Coordination Fragment Modulation and Electroluminescent Performance of Benzimidazole-based Tetradentate Cyclometalated Platinum(II) Complexes

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