卤代苯甲酸-TPTZ铽配合物的合成、表征及荧光性能  

Synthesis,Characterization and Fluorescence Properties of Complexes of Terbium with Halobenzoic Acid and 2,4,6-tris-(2-pyridyl)-s-triazine

作　　者：林雪梅[1] 赵永亮[1] 周永生[1] 孙慧娟[1] 白健[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

出　　处：《发光学报》2011年第3期220-226,共7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：分别以对溴苯甲酸和对碘苯甲酸为第一配体,2,4,6-三吡啶基三嗪(TPTZ)为第二配体,以铽为中心,La3+、Y3+、Gd3+为掺杂离子,合成了8种铽及其掺杂配合物,对其进行了C、H、N元素分析及稀土络合滴定、紫外光谱、红外光谱和荧光光谱测定。推测配合物的组成为:Tb(P-BrBA)3(TPTZ).2H2O和Tb(P-IBA)3-(TPTZ).2H2O;铽掺杂稀土配合物为:Tb0.5Ln0.5(P-BrBA)3(TPTZ).2H2O和Tb0.5Ln0.5(P-IBA)3(TPTZ).2H2O(P-BrBA=对溴苯甲酸,P-IBA=对碘苯甲酸,Ln3+=La3+,Y3+,Gd3+)。摩尔电导率测试结果表明所有配合物均为非电解质。红外光谱测试结果表明,卤代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成键。在上述铽配合物中,对溴苯甲酸配合物的荧光强度高于对碘苯甲酸配合物;掺入荧光惰性稀土离子镧、钆及钇后,发光强度均有不同程度的改变,掺入镧可明显增强铽的发光强度,钆可敏化铽的发光,而钇的敏化作用则不明显。Eight terbium complexes have been synthesized by using p-bromine-benzoic acid,p-iodin-benzoic acid as the first ligand and 2,4,6-tris-（2-pyridyl）-s-triazine（TPTZ） as the second ligand.The ligands and coordination compounds are studied by IR spectra,UV spectra,fluorescence excitation and emission spectra.The results showed that all the complexes are non-electrolytes.P-bromine-benzoic acid or p-iodin-benzoic acid is bounded with Tb（Ⅲ） through oxygen atoms and 2,4,6-tris-（2-pyridyl）-s-triazine is bounded to Tb（Ⅲ） through three nitrogen atoms.Fluorescence emission spectra indicated that the intensity of terbium complexes of p-bromine-benzoic acid is stronger than those of p-iodine-benzoic acid.The fluorescence intensity of terbium complexes are enhanced by introducing La3＋ and Gd3＋ ions,respectively.We also find that when n（Tb）∶n（Ln）=1∶1（Ln=La,Gd,Y）,the fluorescence emission intensity of Tb0.5La0.5（P-BrBA）3（TPTZ）·2H2O,Tb0.5Gd0.5（P-BrBA）3（TPTZ）·2H2O and Tb0.5Y0.5（P-BrBA）3（TPTZ）·2H2O gradually decrease.The fluorescence emission intensity sequence of Tb（Ⅲ） with p-iodin-benzoic acid and TPTZ complexes are similar with the Tb（Ⅲ） with p-bromine-benzoic acid and TPTZ complexes.The 5D4 energy of Tb3＋ ion is 20 430 cm-1,and 21 277 cm-1 for the triplet energy of TPTZ.The triplet energy of TPTZ is higher than the excitation energy of Tb3＋ion,thus the absorbing energy of TPTZ can effectively transferred to Tb3＋ ion,and producing a characteristic emission spectrum.Some complexes of non-fluorescence rare earth can also absorb the triplet energies of the ligands,and then transfer them to Tb3＋,in this way the fluorescence intensity is enhanced.

关 键 词：对溴苯甲酸 对碘苯甲酸 2 4 6-三吡啶基三嗪 铽配合物 

分 类 号：O482.31[理学—固体物理]