新型膦氧类化合物及其铂配合物的合成与发光性能研究
发布时间：2019-02-25 18:07
【摘要】：本文设计合成了一系列新型的膦氧类大位阻化合物以及铂配合物和异核双金属Pt-M配合物。应用核磁、元素分析、X-射线单晶衍射对化合物进行了结构确证,系统研究了化合物的发光性能。通过测定它们的紫外吸收光谱和循环伏安图谱,计算出了化合物的HOMO、LUMO轨道。主要研究内容如下:1、合成了六种新型的苯并咪唑、三氮唑和四氮唑膦氧类化合物(L1-L6),其中,苯并咪唑系列化合物L1,L3,L4都具有较高的发光量子效率,固体发光效率均在50%以上。化合物L1表现出了深蓝色发光,溶液发光效率为45.6%,固体发光效率高达69.4%。苯并咪唑上引入推电子基导致化合物发光增强,吸电子基使化合物发射光谱蓝移。2、以化合物L1-L5为解聚配体、ppy为环金属配体,合成了五种金属Pt(Ⅱ)配合物(Pt-L1~Pt-L5)。Pt(Ⅱ)与L1-L4和ppy分别以N^O、C^N的形式配位,形成平面四边形结构。晶体结构分析证明,分子间没有明显的堆积相互作用。Pt(Ⅱ)与L5和ppy形成双核铂配合物。这五个配合物均表现出长寿命的高效磷光发射,其中配合物Pt-L5的固体发光效率高达77%。配体上取代基的改变对配合物的发射峰位置以及轨道能级影响不大。3、以四氮唑膦氧化合物L6为配体,结合ppy合成了6种新型异核双金属配合物Pt-L6-M(M=Na、Fe、Zn、Mg、Ca、Cd)。其中配合物Pt-L6-Na结构独特,中心Pt(Ⅱ)离子形成了六配位的变形八面体构型。该系列配合物-P=O基团的O原子均未参与铂的配位。这类配合物表现出了非常好的磷光性质,其固体发光效率分别为62.5%、54.2%、54.6%、58.9%、42.8%、41.6%,而溶液发光效率分别为55.4%、94.1%、93.7%、94.2%、89.0%、88.6%。77K下配合物的磷光发射证明,所有铂配合物的磷光发射主要是来自配体三线态(3LC)的辐射跃迁。
[Abstract]:In this paper, we have designed and synthesized a series of novel phosphonoxins, platinum complexes and heteronuclear bimetallic Pt-M complexes. The structure of the compound was confirmed by NMR, elemental analysis and X-ray single crystal diffraction. The luminescent properties of the compound were studied systematically. The HOMO,LUMO orbitals of the compounds were calculated by measuring their UV absorption spectra and cyclic voltammetry. The main contents are as follows: 1. Six new benzimidazole, triazole and tetrazolium phosphine oxide compounds (L1-L6) were synthesized. Among them, benzimidazole series compounds L _ 1, L _ 3, L _ 4 all have high luminescence quantum efficiency. The solid luminescence efficiency is above 50%. The luminescence efficiency of the compound L1 is 45.6% in solution and 69.4% in solid state, and the luminescence efficiency in solution is 45.6% and that in solid state is 69.4%. The introduction of electron-pushing groups on benzimidazole resulted in the enhancement of the luminescence of the compounds. The emission spectra of the compounds were blue-shifted by the electron-absorbing group. The compound L1-L5 was used as the depolymerized ligand and the ppy as the cyclic metal ligand. Five metal Pt (鈪，
本文编号：2430402
[Abstract]:In this paper, we have designed and synthesized a series of novel phosphonoxins, platinum complexes and heteronuclear bimetallic Pt-M complexes. The structure of the compound was confirmed by NMR, elemental analysis and X-ray single crystal diffraction. The luminescent properties of the compound were studied systematically. The HOMO,LUMO orbitals of the compounds were calculated by measuring their UV absorption spectra and cyclic voltammetry. The main contents are as follows: 1. Six new benzimidazole, triazole and tetrazolium phosphine oxide compounds (L1-L6) were synthesized. Among them, benzimidazole series compounds L _ 1, L _ 3, L _ 4 all have high luminescence quantum efficiency. The solid luminescence efficiency is above 50%. The luminescence efficiency of the compound L1 is 45.6% in solution and 69.4% in solid state, and the luminescence efficiency in solution is 45.6% and that in solid state is 69.4%. The introduction of electron-pushing groups on benzimidazole resulted in the enhancement of the luminescence of the compounds. The emission spectra of the compounds were blue-shifted by the electron-absorbing group. The compound L1-L5 was used as the depolymerized ligand and the ppy as the cyclic metal ligand. Five metal Pt (鈪，
本文编号：2430402
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