对氯苯甲酸-2,4,6-三吡啶基三嗪稀土配合物的合成、表征及发光性能  

Synthesis,Characterization and Fluorescence Properties of Rare Earth with p-Chloro-benzoic Acid and 2,4,6-Tris-(2-pyridyl)-s-triazine

作　　者：周永生[1] 赵永亮[1,2] 胥佳颖[1] 杜燕[1] 李欢欢[1] 魏晓燕[1] 马瑞军[1] 

机构地区：[1]内蒙古大学化学化工学院,内蒙古呼和浩特010021 [2]北京大学稀土材料化学及应用国家重点实验室,北京100871

出　　处：《发光学报》2010年第5期661-666,共6页Chinese Journal of Luminescence

基　　金：国家自然科学基金(20461002);内蒙古自然科学基金(200711020203)资助项目

摘　　要：以对氯苯甲酸为第一配体,2,4,6-三吡啶基三嗪(TPTZ)为第二配体,分别以铕、铽和镝为中心,合成了10种稀土配合物,并进行了元素分析、稀土络合滴定、等离子光谱、紫外光谱、红外光谱和发光光谱测定。配合物的组成为:RE(p-ClBA)3(TPTZ).2H2O和RE0.5Ln0.5(p-ClBA)3(TPTZ).2H2O(RE=Eu3+,Tb3,+Dy3+;Ln=La3,+Gd3,+Y3;+p-ClBA=对氯苯甲酸根;TPTZ=2,4,6-三吡啶基三嗪),均为非电解质;对氯苯甲酸的羧基氧原子与稀土离子配位,2,4,6-三吡啶基三嗪以主配位点上的3个氮原子与稀土离子配位;铕配合物的发光强度大于铽配合物的,镝配合物发光最弱;在上述3种发光稀土配合物中分别掺入发光惰性稀土离子镧、钆及钇后,发光强度有不同改变,掺入镧可明显增强铕、铽的发光强度,钆可敏化铕、铽和镝的发光,而钇的敏化作用较弱。表明:掺杂配合物并不完全是两种简单配合物的机械混合,而是有混配配合物生成。In this work,ten complexes of europium,terbium and dysprosium with p-chroro-benzoic acid and 2,4,6-tris-（2-pyridyl）-s-triazine（TPTZ） were synthesized and characterized by elemental analysis,rare earth coordination titration and inductively coupled plasma atomic emission spectrometry（ICP）,the results showed that the complexes have the composition of Eu（p-ClBA）3（TPTZ）·2H2O;Tb（p-ClBA）3（TPTZ）·3H2O and Dy（p-ClBA）3（TPTZ）·2H2O;Eu0.5La0.5（p-ClBA）3（TPTZ）·2H2O,Eu0.5Gd0.5（p-ClBA）3（TPTZ）·2H2O,Eu0.5Y0.5（p-ClBA）3（TPTZ）·2H2O,Tb0.5La0.5（p-ClBA）3（TPTZ）·2H2O Tb0.5Gd0.5（p-ClBA）3-（TPTZ）·2H2O,Tb0.5Y0.5（p-ClBA）3（TPTZ）·2H2O and Dy0.5Gd0.5（p-ClBA）3（TPTZ）·2H2O.The molar conductivity indicated that all the complexes are non-electrolytes.The ligands and the complexes were studied by the means of IR spectra,UV spectra,fluorescence excitation and emission spectra.The results showed that p-chroro-benzoic acid is bonded with rare earth ions through oxygen atoms in the carboxyl group;2,4,6-tris-（2-pyridyl）-s-triazine through the three nitrogen atoms coordinate with the rare earth ions.The red shift in UV Absorption spectra of the complexes is observed,substantiating that a more extensive π-π＊ conjugating system is formed due to the coordinated reaction.The fluorescence emission intensity of Eu（p-ClBA）3（TPTZ）·2H2O is the strongest compare with other two rare earth complexes [Tb（p-ClBA）3-（TPTZ）·3H2O and Dy（p-ClBA）3（TPTZ）·2H2O].But,the fluorescence emission intensity of Tb0.5La0.5-（p-ClBA）3（TPTZ）·2H2O is the strongest in the doped rare earth complexes.The doped rare earth ions（La3＋,Gd3＋ and Y3＋） can sensitize the luminescence of the complexes,it showed that a part of dinuclear complexes are formed.

关 键 词：对氯苯甲酸 2 4 6-三吡啶基三嗪 稀土配合物 掺杂 

分 类 号：O482.3[理学—固体物理]