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外围取代基团对卟啉铂(Ⅱ)配合物发光性能的影响
Effect of Peripheral Substituents on Luminescent Properties of the Porphyrin Platinum( Ⅱ) Complexes
【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%.
【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 to3LC 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;
- 【文献出处】 高等学校化学学报 ,Chemical Journal of Chinese Universities , 编辑部邮箱 ,2014年06期
- 【分类号】O641.4
- 【被引频次】5
- 【下载频次】157