外围取代基团对卟啉铂(Ⅱ)配合物发光性能的影响

doi:10.7503/cjcu20130944

摘要/Abstract

摘要：

设计合成了具有不同外围取代基的卟啉铂(Ⅱ)配合物PtTEMP, PtTBMP, PtOMPP和PtDMPP, 并对其结构和光电性能进行了表征. 晶体结构分析结果表明, 这些卟啉铂(Ⅱ)配合物具有较理想的平面配位构型, β-位叔丁基的引入有效抑制了分子间的π-π相互作用. 外围取代基几乎不影响配合物的吸收和发光性质, 最大发射峰位于646~656 nm之间, 为配体中心的 ³π^*-π磷光发射. 空间位阻效应更强的叔丁基取代配合物(PtTBMP)的溶液态荧光量子效率和外量子效率最高, 分别为0.58和6.3%. 3个甲氧基取代的PtDMPP的发光效率优于2个甲氧基取代的PtOMPP, 二者的溶液态荧光量子效率分别为0.36和0.29, 外量子效率分别为2.4%和1.7%.

关键词: 卟啉铂(Ⅱ)配合物, 取代基, 分子间相互作用, 位阻效应, 电致发光

Abstract:

Porphyrin platinum(Ⅱ) complexes with efficient red phosphorescent emission have attracted extensive interest due to their potential application in the organic light emitting diodes(OLEDs). However, the strong π-π intermolecular interactions derived from their rigid planar coordination geometry result in the occurrence of self-quenching and affect their performance. In this work, a series of porphyrin platinum(Ⅱ) complexes with different peripheral substituents(PtTEMP, PtTBMP, PtOMPP and PtDMPP) were designed, synthesized and characterized, for the purpose of effectively restraining the intermolecular π-π interaction. Single crystal X-ray structure analysis indicated that they had ideal square-planar geometry around Pt atom, and bulky t-butyl substituent could inhibit effectively π-π interactions. The peripheral substituents hardly affected absorption and emission properties of the complexes, and the luminescent peaks at 646—656 nm were assigned to ³LC phosphorescent emission. PtTBMP showed the highest emission quantum yield(0.58) and external quantum efficiency(EQE, 6.3%) due to strong steric effect of t-butyl. The luminous efficiency of PtDMPP with three methoxyl substitutents was better than PtOMPP with two methoxyl, the corresponding emission quantum yield were 0.36 and 0.29, and were 2.4% and 1.7%, respectively. The results indicated that the encapsulating effect of the peripheral substituents could improve luminescent efficiency of porphyrin platinum(Ⅱ) complexes.

Key words: Porphyrin platinum(Ⅱ) complex, Substituent, Intermolecular interaction, Hindrance effect, Electroluminescent

中图分类号:

O621.22

TrendMD:

袁伟, 任清江, 孙恒达, 李慧, 程延祥, 马东阁. 外围取代基团对卟啉铂(Ⅱ)配合物发光性能的影响. 高等学校化学学报, 2014, 35(6): 1229.

YUAN Wei, REN Qingjiang, SUN Hengda, LI Hui, CHENG Yanxiang, MA Dongge. Effect of Peripheral Substituents on Luminescent Properties of the Porphyrin Platinum(Ⅱ) Complexes^†. Chem. J. Chinese Universities, 2014, 35(6): 1229.

图/表 7

Fig.1 Molecular structures of ligands(A) and porphyrin platinum(Ⅱ) complexes(B)

Fig.2 ORTEP drawings(30% probability ellipsoids)(A, B) and packing structures(A1, B1, B2) of PtTEMP(A, A1) and H2TBMP(B, B1, B2) H atoms are omitted for clarity.

Fig.3 Normalized UV-Vis absorption(solid) and PL spectra(dash) of ligands(A) and corresponding

Table 1 Photophysical data of porphyrin ligands and corresponding platinum(Ⅱ) complexes

Compound	λ_abs/nm/lgε^a	$λ em a$ /nm	τ^b/μs	$Φ PL b, c$	10^-4 $k r d$ /s^-1	10^-4 $k nr d$ /s^-1
H₂TEMP	396/5.56; 497/4.55; 526/4.43; 568/4.32; 621/4.28	620, 689	0.017
H₂TBMP	402/5.76; 501/4.65; 534/4.48; 572/4.35; 627/4.32	626, 691	0.021
H₂OMPP	417/5.84; 512/4.57; 541/4.04; 589/4.11; 645/3.85	650, 709	0.019
H₂DMPP	420/6.07; 514/4.81; 546/4.30; 590/4.30; 646/4.04	652, 711	0.015
PtOEP	378/5.49; 500/4.17; 534/4.87	648	74	0.45	0.61	0.74
PtTEMP	380/5.74; 500/4.23; 534/4.61	646	15	0.43	2.86	3.81
PtTBMP	380/5.88; 500/4.37; 534/4.78	656	34	0.58	1.71	1.23
PtOMPP	400/5.60; 508/4.58; 540/4.69	656, 712	40	0.29	0.73	1.78
PtDMPP	404/5.65; 510/4.28; 540/4.77	654, 710	57	0.36	0.63	1.12

Table 1 Photophysical data of porphyrin ligands and corresponding platinum(Ⅱ) complexes

Compound	λ_abs/nm/lgε^a	$λ em a$ /nm	τ^b/μs	$Φ PL b, c$	10^-4 $k r d$ /s^-1	10^-4 $k nr d$ /s^-1
H₂TEMP	396/5.56; 497/4.55; 526/4.43; 568/4.32; 621/4.28	620, 689	0.017
H₂TBMP	402/5.76; 501/4.65; 534/4.48; 572/4.35; 627/4.32	626, 691	0.021
H₂OMPP	417/5.84; 512/4.57; 541/4.04; 589/4.11; 645/3.85	650, 709	0.019
H₂DMPP	420/6.07; 514/4.81; 546/4.30; 590/4.30; 646/4.04	652, 711	0.015
PtOEP	378/5.49; 500/4.17; 534/4.87	648	74	0.45	0.61	0.74
PtTEMP	380/5.74; 500/4.23; 534/4.61	646	15	0.43	2.86	3.81
PtTBMP	380/5.88; 500/4.37; 534/4.78	656	34	0.58	1.71	1.23
PtOMPP	400/5.60; 508/4.58; 540/4.69	656, 712	40	0.29	0.73	1.78
PtDMPP	404/5.65; 510/4.28; 540/4.77	654, 710	57	0.36	0.63	1.12

Table 2 EL performance of porphyrin platinum(Ⅱ) complexes(8% complexes in TCTA)*

Compound	V_on/V	B_max/(cd·m^-2)	η_c/(cd·A^-1)	η_P/(lm·W^-1)	EQE(%)	λ_max/nm	CIE(x, y)
PtOEP	4.0	271	2.14	1.98	5.8	648	(0.71, 0.28)
PtTEMP	4.2	247	1.73	1.56	4.3	648	(0.70, 0.28)
PtTBMP	4.0	412	2.21	1.98	6.3	648	(0.71, 0.28)
PtOMPP	4.3	457	0.42	0.36	1.7	665, 731	(0.65, 0.27)
PtDMPP	4.2	656	0.46	0.37	2.4	665, 733	(0.52, 0.25)

Fig.4 EL spectra(A) and EQE vs. current density(B) of the devices(8% complexes in TCTA)

Fig.5 EQE vs. doping concentration of complexes at the same current density(10 mA/cm2)

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