非对称双极性Ir(III)配合物磷光分子及其聚集诱导磷光和电致发光性能研究

doi:10.6023/cjoc202403052

摘要/Abstract

同时以功能化的2-苯基吡啶(ppy)类配体和2-乙烯吡啶(vpy)类配体设计合成了两个非对称Ir(III)配合物磷光分子, 并对其光电性能进行了详细表征. 光物理研究表明, 这两个非对称Ir(III)配合物磷光分子具有两种发光激发态产生磷光发射, 并且能够表现出明显的聚集诱导/增强磷光发光行为. 电化学研究结果表明, 功能基团的引入可使非对称Ir(III)配合物磷光分子表现出双极性. 此外, 它们还能表现出较好的电致发光性能, 电致发光器件启亮电压(V_turn-on)小于3 V, 最大亮度L_max为11380 cd•m^－2、最大外量子效率η_ext为5.3%、最大电流效率η_L为12.9 cd•A^－1及最大功率效率η_P为13.6 lm•W^－1. 相关研究结果为新型聚集诱导磷光电致发光材料的设计合成提供了有价值的参考.

关键词: 非对称结构, Ir(III)磷光配合物, 聚集诱导磷光, 双极性, 电致发光

Two unsymmetric Ir(III) phosphorescent complexes have been prepared with functionalized both 2-phenyl- pyridine (ppy)- and 2-vinylpyridine (vpy)-type ligands to investigate their optoelectronic properties. Photophysical results show that there are two kinds of radiative excited states contributing their phosphorescent emission. In addition, the unsymmetric Ir(III) phosphorescent complexes can exhibit aggregation-induced/enhanced phosphorescent emission behavior. Electrochemical results indicate that introducing functional group can confer ambipolar features to the unsymmetric Ir(III) phosphorescent complexes. In addition, they can show decent electroluminescent ability with turn-on voltage (V_turn-on) less than 3.0 V, maximum luminescence (L_max) of 11380 cd•m^－2, maximum external quantum efficiency (η_ext) of 5.3%, maximum current efficiency (η_L) of 12.9 cd•A^－1 and maximum power efficiency (η_P) of 13.6 lm•W^－1. All these results can provide valuable information for design and synthesis of new electroluminescent materials with aggregation-induced phosphorescent emission ability.

Key words: unsymmetric structure, Ir(III) phosphorescent complexes, aggregation-induced phosphorescent emission, ambipolar features, electroluminescence

引用此文

陈姿仪, 刘思琪, 冯钊, 钟道昆, 杨晓龙, 孙源慧, 徐先彬, 冯震, 岳岭, 周桂江. 非对称双极性Ir(III)配合物磷光分子及其聚集诱导磷光和电致发光性能研究[J]. 有机化学, 2024, 44(8): 2563-2570.

Ziyi Chen, Siqi Liu, Zhao Feng, Daokun Zhong, Xiaolong Yang, Yuanhui Sun, Xianbin Xu, Zhen Feng, Ling Yue, Guijiang Zhou. Unsymmetric Phosphorescent Ir(III) Complexes with Ambipolar Features and Investigation for Both Aggregation-Induced Phosphorescent Emission and Electroluminescent Properties[J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2563-2570.

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图/表 13

图式1. 非对称Ir(III)配合物磷光分子的合成路线

Scheme 1. Synthetic scheme of the unsymmetric Ir(III) phosphorescent complexes

Complex	λ_abs^a/nm	λ_em^a/nm (solution/film)	Φ_P^b/% (solution/film)	τ_p^c/μs (solution/film)	T_d/℃
Ir-SO	290 (4.33), 300 (4.33), 386 (4.22), 403 (4.21), 466 (3.68)	568^sh, 661/566, 605^sh	4.3/23.6	0.10 (568 nm), 0.31 (661 nm)/ 0.68 (566 nm)	375
Ir-PO	288 (4.28), 301 (4.27), 387 (4.17), 403 (4.15), 465 (3.57)	570^sh, 648/564, 602 ^sh	10.4/25.2	0.15 (570 nm), 0.43 (648 nm)/ 0.78 (564 nm)	362

表1. 非对称Ir(III)配合物磷光分子的光物理及热学数据

Table 1. Photophysical and thermal data of these unsymmetric Ir(III) phosphorescent complexes

图1. 非对称Ir(III)配合物磷光分子在CH2Cl2溶液中的紫外-可见吸收光谱

Figure 1. UV-vis absorption spectra of the unsymmetric Ir(III) phosphorescent complexes in CH2Cl2

图2. 非对称Ir(III)配合物磷光分子的关键前线分子轨道分布图(等值面=0.030)

Figure 2. Key frontier molecular orbital (MO) patterns (isocontour value=0.030) of the unsymmetric Ir(III) phosphorescent complexes

图3. 非对称Ir(III)配合物磷光分子在CH2Cl2溶液及掺杂薄膜中的发射光谱

Figure 3. Photoluminescence (PL) spectra of the unsymmetric Ir(III) phosphorescent complexes in both CH2Cl2 and doped film

图4. 基于非对称Ir(III)配合物磷光分子T1态优化构型的自然跃迁轨道分布图(等值面=0.030)

Figure 4. Natural transition orbital (NTO) patterns (isocontour value=0.030) for the unsymmetric Ir(III) phosphorescent complexes on the basis of their optimized T1 geometries

Complex	NTO	Contribution percentage of metal d_π orbitals and π orbitals of ligand to NTO
Ir-SO		Ir	L-FN	L-SO	acac
	Hole	16.80%	77.26%	2.72%	2.3%
	Particle	6.20%	15.76%	75.77%	1.23%
Ir-PO		Ir	L-FN	L-SO	acac
	Hole	47.45%	27.43%	16.16%	7.93%
	Particle	13.64%	23.2%	52.59%	3.66%

表2. 基于非对称Ir(III)配合物磷光分子T1态优化构型的自然跃迁轨道数据

Table 2. NTO results for these unsymmetric Ir(III) complexes based on their optimized T1 geometries

图5. 非对称Ir(III)配合物磷光分子(a) Ir-SO和(b) Ir-PO在二氯甲烷-正己烷混合溶剂中的PL光谱

Figure 5. PL spectra of these unsymmetric Ir(III) phosphorescent complexes (a) Ir-SO and (b) Ir-PO in the mixture of CH2Cl2-hexane

Complex	E_pa^a/V	E_pc/V	E_HOMO^c/eV	E_LUMO^d/eV
Ir-SO	0.36, 0.67	－1.97^a, －2.31^a, －2.71^b	－5.16	－2.83
Ir-PO	0.36, 0.65	－2.37^b, －2.49^b, －2.63^b	－5.16	－2.43

表3. 非对称Ir(III)配合物磷光分子的氧化还原特性

Table 3. Redox properties of the unsymmetric Ir(III) phosphorescent complexes

图6. 电致发光器件在5 V电压下的电致发光光谱

Figure 6. EL spectra of the EL devices at 5 V

图7. 优化器件A2和B2的电流-电压-亮度曲线

Figure 7. Current density-voltage-luminance curves for the optimized devices A2 and B2

Device	Dopant	V_turn-on/V	L_max/(cd•m^－2)	η_ext/%	η_L/(cd•A^－1)	η_P/(lm•W^－1)	λ_max/nm
A1	Ir-SO (w=4.0%)	2.6	7527	2.2	4.7	4.8	568 (0.53, 0.45)
A2	Ir-SO (w=6.0%)	2.7	7974	3.2	7.5	8.1	568 (0.53, 0.45)
A3	Ir-SO (w=8.0%)	2.6	7902	2.5	5.5	5.7	568 (0.55, 0.45)
B1	Ir-PO (w=4.0%)	2.7	4865	3.8	9.9	10.3	568 (0.50, 0.47)
B2	Ir-PO (w=6.0%)	2.6	11380	5.3	12.9	13.6	568 (0.53, 0.46)
B3	Ir-PO (w=8.0%)	2.6	7739	4.9	12.0	13.7	568 (0.51, 0.46)

表4. 基于非对称Ir(III)配合物磷光分子OLEDs的最高电致发光数据

Table 4. Maximum EL data achieved by the OLEDs based on the unsymmetric Ir(III) phosphorescent complexes

图8. 优化器件A2 (a)和B2 (b)的电致发光效率-亮度曲线

Figure 8. Relationship between EL efficiencies and luminance for the optimized devices A2 (a) and B2 (b)

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