铕及其掺杂稀土噻吩乙酸、邻菲啰啉配合物的合成、表征及荧光性能  

Studies on Fluorescence Property of Eu^(3+) Dinuclear Complexes with 2-Thiopheneacetic Acid and o-Phenanthroline

作　　者：张梅[1] 赵永亮[1] 赵艳芳[1] 王艳[1] 李海燕[1] 魏晓燕[1] 刘润花[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》2008年第5期827-832,共6页Chinese Journal of Luminescence

基　　金：国家自然科学基金(20461002);教育部春晖计划基金(Z2004-2-15029);内蒙古自然科学基金(200711020203)资助项目

摘　　要：合成了十种以2-噻吩乙酸(TPAC)、邻菲啰啉(Phen)为配体,单一稀土Eu3+配合物、Eu3+掺杂La3+、Gd3+、Y3+、Er3+以及不同比例的Eu3+掺杂La3+异核配合物。进行了元素分析、摩尔电导、热谱、红外光谱、核磁共振及荧光性能研究。配合物的组成分别为EuL3L′,Eu0.5Y0.5L3L′,Eu0.5La0.5L3L′,Eu0.5Gd0.5L3L′,Eu0.5Er0.5L3L′和EuxLa1-xL3L′(其中L=TPAC,L′=Phen)。羧酸的氧原子和邻菲啰啉的氮原子与稀土离子配位,配合物为非电解质。荧光光谱的测试表明荧光惰性离子La3+、Gd3+、Y3+对Eu3+的荧光有增强作用,顺序为La3+>Gd3+>Y3+;Er3+对Eu3+的荧光有猝灭作用。不同比例Eu3+掺杂La3+异核配合物中,当Eu3+:La3+=0.50:0.50时敏化作用最强,荧光强度值最大。Five solid complexes of rare earth Eu^3＋ doped La^3＋ , Gd^3＋ , y3~ , Er^3＋ and five different proportion co-doped complexes（ Eu^3＋ ： La^3＋ ） with 2-thiopheneacetic acid and o,phenanthroline have been synthesized and characterized. Elemental analysis, rare earth coordination titration and TG-DTA studies show that the complexes have the composition of Eu （TPAC）3Phen. The different dinuclear complexes are composed of Eu0.5RE0.5（TPAC）3Phen（RE^3＋ =La^3＋ ,Gd^3＋ ,Y^3＋ ,Er^3＋ ） ; （EuxLay） （TPAC）3Phen （x： y =0.10： 0.90; 0.30：0.70 ;0.40：0.60 ;0.70：0.30 ;0.90： 0.10）. The molar conductivity indicates that all the complexes are nonelectrolyte; IR spectra and ^1H NMR spectra show that 2-thiopheneacetic acid combined as the form of bridging dissymmetrical bidentate ligand, and the two nitrogen atoms in phen are also involved in the rare earth ion coordination for europium complex and its doped with La3＋ , Gd^3＋ , Er^3＋ and Y^3＋ complexes. There are strong fluorescence intensity for all these complexes, it shows that the lowest excitation state energy level of Eu^3＋ ion with the triplet state energy level of the ligands match well each other. Its fluorescence intensity is enhanced after doping with La^3＋ , Gd^3＋ , y^3 ＋. The sensitization actions from La^3＋ , Gd^3＋ , and Y^3＋ to Eu^3＋ ion are Y^3＋ 〈 Gd^3＋ 〈 La^3＋. But Er^3 ＋ make the fluorescence intensity of the europium complex weaken. We also find that as n （Eu） ： n （La） = 1 ： 1, the fluorescence intensity is the strongest in the complexes of （EuxLal-x ） （TPAC）3Phen . 5 Do energy level of Eu^3＋ is 17 250 cm^- 1, the triplet state energy of 2-thiopheneacetic acid and o-phenanthroline are 25 000 cm^-1 and 22 123 cm^-1, respectively. The triplet state energy of the two ligands are higher than the excitation energy of Eu^3＋ ion, thus it is possible that energy transfer from 2- thiopheneacetic acid and o-phenanthroline to Eu^3＋ through-COO-Eu-OOC- and -N--E

关 键 词：2-噻吩乙酸 邻菲哕啉 铕配合物 荧光 

分 类 号：O482.31[理学—固体物理]