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

doi:10.6023/A26050148

化学学报 ›› 2026, Vol. 84 ›› Issue (8): 1236-1242.DOI: 10.6023/A26050148 上一篇下一篇

研究论文

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
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: *E-mail: shenyue@syuct.edu.cn; lnq0518@suit-sz.edu.cn
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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1. Supporting Information-A26050148.pdf(1922KB)

摘要/Abstract

环金属铂(Ⅱ)配合物凭借优异的激子利用率与结构可修饰性, 是高性能磷光有机发光二极管(OLEDs)的核心客体材料. 本工作以刚性苯并咪唑并苯并咪唑(BZI)为基本构筑单元, 分别引入吡啶与苯并噻唑片段, 设计并制备了两种四齿环金属铂(II)配合物Pt-py与Pt-bt. 两者均具备优异的热力学与电化学稳定性. 以Pt-py为客体制备的掺杂电致发光器件, 其最大发射波长、亮度、电流效率、功率效率与外量子效率分别为523 nm、65782 cd•m⁻²、83.3 cd•A⁻¹、86.5 lm•W⁻¹与23.4%, 且在1000 cd•m⁻²亮度下效率滚降仅为4.7%. 相比之下, Pt-bt基器件最大外量子效率仅为10.4%, 但其实现发射光谱红移, 成功将光色调控至橙红光区. 上述结果表明, BZI刚性基团为铂(II)配合物高效磷光发射提供了结构基础, 而通过合理选择配位片段, 可在发光颜色、效率以及稳定性之间进行调控, 为新型四齿铂(II)基磷光材料的分子设计与OLEDs应用提供参考.

关键词: 环金属铂(II)配合物, 电致发光, 苯并咪唑, 吡啶, 苯并噻唑

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

引用此文

黄宏, 邓德朋, 卢丹, 申月, 李能泉, 张友明, 华涛, 任保轶. 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[J]. 化学学报, 2026, 84(8): 1236-1242.

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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图/表 8

图1. 配合物Pt-py和Pt-bt的分子结构

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

图2. Pt-py和Pt-bt配合物基态的(a)分子结构正视图和侧视图, (b) S0、S1和T1的几何比较和RMSD值, (c)前线轨道分布以及能量和(d) T1→S0态的自然跃迁轨道

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

图3. 配合物Pt-py与Pt-bt在二氯甲烷溶液中的归一化紫外-可见吸收光谱与光致发光光谱

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

表1. Pt-py和Pt-bt的光物理性质、电化学与热力学性质

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

图4. 配合物Pt-py与Pt-bt在掺杂浓度为5%的DMIC-TRZ薄膜中的瞬态光谱

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

图5. 配合物Pt-py与Pt-bt的循环伏安曲线

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

图6. 基于Pt-py和Pt-bt的掺杂OLEDs电致发光性能. (a)归一化EL光谱; (b)电流密度-电压-亮度曲线; (c)外部量子效率-亮度曲线; (d)电流效率-亮度-功率效率曲线

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)

表2. 基于Pt-py和Pt-bt掺杂OLEDs的电致发光性能

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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