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Zn(Ⅱ)/Cu(Ⅱ)和稀土配合物的合成、表征及发光性能的研究

Synthesis, Characterization and Fluorescent Studies of Zn(Ⅱ) / Cu(Ⅱ) and Rare Earth Complexes

【作者】 张冬梅

【导师】 沈应中;

【作者基本信息】 南京航空航天大学 , 有机化学, 2010, 硕士

【摘要】 有机电致发光是近年来国际上的一个研究热点。在众多的有机发光材料中,腙类化合物是一类具有良好光学性能的化合物,在有机电致发光材料中具有潜在的应用价值;稀土金属配合物因其荧光量子效率高、发光谱带窄、色度纯,是一类具有特殊发光性能和物理性质的电致发光材料,而使它们的研究越来越受到人们的重视。本文采用苯甲酰肼分别与β-萘乙酮、邻硝基苯甲醛、对溴苯乙酮、二苯甲酮进行缩合反应,合成了四个酰腙配体:β-萘乙酮缩苯甲酰腙(a)、邻硝基苯甲醛缩苯甲酰腙(b)、对溴苯乙酮缩苯甲酰腙(c)、二苯甲酮缩苯甲酰腙(d);a分别与Zn(OAc)2·2H2O、Cu(OAc)2·H2O;b、c分别与Cu(OAc)2·H2O在甲醇中反应,合成了四个新的酰腙金属二元配合物。通过元素分析、红外光谱、紫外光谱、核磁共振氢谱、核磁共振碳谱、单晶X射线衍射分析等手段表征,配合物的组成符合如下分子式:[M(L)2] [L = a, M = Zn(II) (a1), Cu(II) (a2); L = b, M = Cu(II) (b1); L = c, M = Cu(II) (c1)]。研究了金属离子种类、配体结构对配合物荧光强度的影响。采用循环伏安法对配合物a1进行了能带参数的测定。此外,本文还采用β-萘甲酰苯甲酰甲烷(β-HNBM)为第一配体、5,6-二酮-1,10-邻菲啰啉(QPT)为第二配体,并将它们分别与铕及稀土掺杂金属在乙醇中反应,合成了十四种未见文献报道的掺杂稀土金属配合物。元素分析及稀土络合滴定的测试结果表明,三元配合物的组成符合如下分子式:Eu(β-NBM)3QPT;异核配合物的组成为:Eu0.5RE0.5(β-NBM)3QPT (RE = Er3+, Nd3+, Ce3+, Dy3+, Y3+, Lu3+) ;不同掺杂比例配合物的组成为: Eu1-xYx(β-NBM)3QPT和Eu1-xLux(β-NBM)3QPT (x = 0.10, 0.30, 0.50, 0.70, 0.90)。本文采用不同比例的掺杂稀土来研究最佳效果的荧光,最后根据配合物的光致发光性能(荧光光谱),探讨了它们作为电致发光材料的应用前景。

【Abstract】 Organic electroluminescence (OEL) materials have become a fascinating research field in recent years because of their potential applications in panel displayer. With satisfactory light function, the compounds of hydrazone have potential applications in OEL materials. Rare earth (RE) complexes are a kind of electroluminescence materials with special light and physical properties among many OEL materials. They have been payed more and more attention from many investigators due to their high fluorescence efficiency, narrow bandwidth and good purity of light. Four novel complexes of type [M(L)2] [L = 2-acetonaphthonebenzoylhydrazone (a), M = Zn(II) (a1), Cu(II) (a2); L = 2-nitrobenzaldehydebenzoylhydrazone (b), M = Cu(II) (b1); L = 4’-bromoacetophenonebenzoylhydrazone (c), M = Cu(II) (c1).] have been synthesized conveniently by the reactions of zinc(II) acetate dihydrate/copper(II) acetate monohydrate with appropriate hydrazone ligands which were synthesized by condensation reactions of benzhydrazide with aldehyde or ketone in methanol. The complexes obtained have been characterized by elemental analysis, IR, UV, 1H NMR, 13C{H} NMR and Single crystal X-ray analysis. The influences of different metal ions and different ligands on luminescent properties of complexes have been studied. The energy-band parameters of complex a1 have been explored by cyclic voltammetry. Furthermore, fourteen new RE complexes have been prepared by usingβ-naphthoylbenzoylmethane (β-HNBM), 5,6-quinone-l,10-phenanthroline (QPT) and different rare ions. Elemental analysis and RE coordination titration indicate that the composition of ternary complex is Eu(β-NBM)3QPT; the composition of the series of Eu3+ doped with different RE ions has this type molecular formula: Eu0.5RE0.5(β-NBM)3QPT (RE = Er3+, Nd3+, Ce3+, Dy3+, Y3+, Lu3+); there are two groups of the series of Eu3+ complexes doped with different proportional RE ions, namely, Eu1-xYx(β-NBM)3QPT and Eu1-xLux(β-NBM)3QPT (x = 0.10, 0.30, 0.50, 0.70, 0.90). The best fluorescence intensity has been studied in this thesis according to different proportional doped RE ions. According to photoluminescence (fluorescence spectra), the electroluminescence properties of the complexes have been discussed.

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