【作者】 张瑞平；

【导师】 李文先；

【作者基本信息】 内蒙古大学 ， 无机化学， 2005， 硕士

【摘要】 本文采用低温固相合成法,以稀土氯化物、1—萘甲酸（HL₁）、苯甲酸（HL₂）、苯乙酸（HL₃）、苯羟乙酸（HL₄）为原料,以六次甲基四胺为质子受体,合成并表征了四个系列十六种固态配合物。经元素分析、稀土络合滴定及热重分析,表明配合物的组成分别为:RE（L₁）₃·nH₂O（n=0～1）、RE（L₂）₃·nH₂O（n=0.5～1.5）、RE（L₃）₃·nH₂O（n=0.5～1.5）和RE（L₄）₃·4H₂O（RE=La,Nd,Eu,Tb）。红外光谱、核磁共振氢谱表明,1—萘甲酸稀土配合物中配体通过羧基以不对称桥式双齿的方式与稀土离子（Ⅲ）配位成键;苯甲酸稀土配合物中配体通过羧基以螯合—桥式三齿的方式与稀土离子（Ⅲ）配位成键;苯乙酸稀土配合物中配体通过羧基以对称螯合双齿的方式与稀土离子（Ⅲ）配位成键;苯羟乙酸稀土配合物是配体以羧基氧负离子和醇羟基同时参与稀土离子（Ⅲ）配位,还有两分子水也参与稀土的配位。二甲亚砜溶液中测定的摩尔电导率表明,所有配合物在二甲亚砜溶剂中均以非电解质形式存在。各系列铕（Ⅲ）、铽（Ⅲ）配合物的荧光光谱和配体的磷光光谱表明,各配体对铕（Ⅲ）、铽（Ⅲ）的荧光都具有一定的敏化作用,但荧光强度不一样,这表明配体的三重态能级和配合物结构的差异都是影响配合物发光的重要因素。SEM照片显示,La（L₂）₃·0.5H₂O的形状与一维纳米棒接近。更多还原

【Abstract】 Four series and sixteen solid complexes of rare earth chloride with 1-naphthoic acid （L₁）,benzoic acid （L₂）,phenylacetic acid （L₃） and Mandelic acid （L₄） have been synthesized by method of solid state reaction at low temperature,and then these complexes were characterized by chemical analysis methods. Elemental analysis, rare earth coordination titration and TGA studies suggest that the composition of the complexes is RE（L₁）₃ · nH₂O （n=0¹） ,RE（L₂）₃ · nH₂O （n= 0.5-1.5） ,RE（L₃）₃· nH₂O （n=0.5¹.5） and RE（L₄）₃· 4H₂O （RE=La, Nd, Eu, Tb） respectively. IR spectra and 1HNMR studies indicated that the coordinationfashion of four ligands with RE（III） is different. The ligand（L₁） is bonded with RE（III） ions by two oxygen atoms in carboxyl group which coordinate as an asymmetrical bridging bidentate group. The ligand（L₂） is bonded with RE（III） ions by two oxygen atoms in carboxyl group which coordinate as a chelate-bridging tridentate group. The ligand（L₃） is bonded with RE（III） ions by two oxygen atoms in carboxyl group which coordinate as a symmetrical chelate bidentate group. The ligand （L₄） is bonded with RE（III） ions by the one oxygen atom in the carboxyl group and the oxygen atom in the hydroxyl group. The Molar conductivity in DMSO solvent indicates that all complexes are non-electrolyte. Fluorescence spectra of Eu³⁺ and Tb³⁺ complexes and Phosphorescence Spectra of ligands show that all of four ligands have sensitized differently RE³⁺ ions in fluorescence intensity. It indicates that the triplet state energy of ligands and the different structure of complexes play an important role in luminescence of complexes. The four products are measured by SEM. The images indicate that particle diameter and the shape of La（L2）3 ? O.5H2O are similar to one dimensional nanometer stick.更多还原