苯甲酸及其衍生物与1,10-邻菲咯啉铽的三元配合物的荧光光谱研究

Studies on Luminescence Properties of Seven Ternary Complexes of Terbium with 1,10-Phenanthroline and Benzoic Acid and Its Derivatives

分别以苯甲酸及邻、间、对甲基(甲氧基)苯甲酸为第一配体,以邻菲咯啉(phen)为第二配体,合成了七种Tb(Ⅲ)的三元配合物。通过元素分析确定了各配合物的组成。在室温下,测定了各固体配合物的激发和发射光谱,讨论了不同种类、不同位置的取代苯甲酸作第一配体对铽三元配合物荧光性质的影响。结果表明,取代苯甲酸作第一配体的Tb(Ⅲ)三元配合物的最佳发射峰5D4→7F6(489 nm),5D4→7F5(545 nm)的强度,均比苯甲酸作配体的配合物强。甲基为取代基的苯甲酸的三种配合物中,最佳发射峰的强度顺序为:Tb(o-MBA)3phen<Tb(m-MBA)3phen.H2O<Tb(p-MBA)3phen(其中o-MBA为邻甲基苯甲酸根、m-MBA为间甲基苯甲酸根、p-MBA为对甲基苯甲酸根、phen为邻菲咯啉);甲氧基为取代基的苯甲酸的三种配合物中,最佳发射峰强度顺序为:Tb(o-MOBA)3phen.H2O>Tb(m-MOBA)3phen.H2O>Tb(p-MOBA)3phen(其中o-MOBA为邻甲氧基苯甲酸根、m-MOBA为间甲氧基苯甲酸根、p-MOBA为对甲氧基苯甲酸根)。

Seven ternary complexes of Tb（Ⅲ） were synthesized with benzoic acid（BA）, o-, m-, p-methylbenzoic acid （o-MBA, m-MBA, p-MBA）, and o-, m-, p-methoxybenzoic acid（o-MOBA, m-MOBA, p-MOBA） as the first ligand, and 1,10-phenanthroline（phen） as the second ligand. The content of C, H and N were measured by using a Flash-EA model 1112 elemental analyzer. Excitation and luminescence spectra of the title solid complexes were recorded by using a Hitachi F-4500 fluorescence speetrophotometer at room temperature. The effects of different varieties and different positions of replacing benzoic acid as the first ligand on fluorescence properties of the ternary complexes of terbium were discussed. The results indicated that the intensity of ^5D4→^7F6 （489 nm） and ^5D4→^7F5 （545 nm） of substituting benzoic acid complexes was stronger than benzoic acid. Three ternary complexes of Tb（Ⅲ） with o-, m-, p-methylbenzoic acid showed emission intensity in the consecution： Tb（o-MBA）3 phen〈Tb （m-MBA）3 phen· H2O〈Tb（pMBA）3phen. However, for the complexes with o-, m-, p-methoxybenzoic acid as the first ligand： Tb（o-MOBA）3 phen · H2O〉Tb（m-MOBA）3 phen · H2O〉Tb（pMOBA）3 phen.