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

作　　者：袁伟[1,2] 任清江[1] 孙恒达 李慧[1] 程延祥[1] 马东阁[1] 

机构地区：[1]中国科学院长春应用化学研究所高分子物理与化学国家重点实验室,长春130022 [2]中国科学院大学,北京100049

出　　处：《高等学校化学学报》2014年第6期1229-1235,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21204083;51073152)资助~~

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%.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 3 LC 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.

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 

分 类 号：O621.22[理学—有机化学]