新的稀土Eu,Tb(Ⅲ)β-二酮三元配合物的合成与光谱性质  

Synthesis and Photoluminescence Properties of New Europium,Terbium(Ⅲ) Ternary Complexes Based on β-diketone

作　　者：程果[1] 魏长平[1] 任晓明[1] 王贺[1] 

机构地区：[1]长春理工大学化学与环境工程学院,吉林长春130022

出　　处：《中国稀土学报》2012年第2期157-162,共6页Journal of the Chinese Society of Rare Earths

基　　金：吉林省教育厅"十一五"科技项目(201028;201034)资助

摘　　要：采用Claisen缩合反应合成了一种β-二酮1-(4-氨基苯)-3-苯基丙烷-1,3-二酮(L:C15H13NO2),以元素分析和1H NMR谱确定了其组成,核磁和红外分析结果表明L主要以烯醇式存在。以L为第一配体,分别以邻菲罗啉(phen),2,2'-联吡啶(bipy)为第二配体,合成了新的稀土Eu,Tb(Ⅲ)三元配合物。通过元素分析、红外光谱、紫外光谱、磷光光谱和荧光光谱对合成的配合物进行了表征。荧光光谱表明:稀土铽配合物的发光性能优于稀土铕配合物,进一步研究表明配体L与Tb3+间能级差较匹配,分子内传能效率高;phen对配合物的荧光敏化效果优于bipy,表明第二配体的刚性和共轭性越大,配合物的发光性能越好。The β-diketone 1-（4-aminophenyl）-3-phenylpropane-1,3-dione（L） was synthesized by classical Claisen condensation reaction,and the composition of the β-diketone L was confirmed by elemental analysis and 1H NMR spectra.The result of 1H NMR spectra indicated that the ligand L existed as an enol form isomer,which was consistent with the result of IR analysis.With L as the first ligand and 1,10-phenanthroline（phen） or 2,2′-bipyridin（bipy） as the secondary ligand,four new rare-earth Eu,Tb（Ⅲ） ternary complexes were prepared in ethanol solution.The ligand L and ternary complexes were characterized by elemental analysis,1H NMR spectra,IR spectra,UV-vis spectra,phosphorescence spectra and fluorescence spectra.IR spectra indicated that： the rare-earth ion in the ternary complexes was coordinated with six oxygen atoms of three L ligands and two nitrogen atoms of the second ligand.The UV-vis spectra showed that the main absorption was from the ligand L in the ternary complexes.The fluorescence spectra demonstrated that the complexes could emit characteristic fluorescence of rare-earth ion and the strongest emission band was narrow which was attributed to the transitions of the 4f electrons of the central ions.The fluorescence intensity of Tb（Ⅲ） ternary complexes was obviously higher than that of Eu（Ⅲ） ternary complexes,and this indicated that the energy level difference between the triplet state of ligand L and the emission energy of Tb3＋ was well matched.The fluorescence spectra also showed that the phen was a better secondary ligand than bipy.So,the Tb（L）3phen exhibited the highest emission than others.It is an excellent green-emitter which would be regarded as a valuable material with bright green fluorescence.

关 键 词：稀土配合物 Β-二酮 合成 光谱性质 能级 

分 类 号：O614.33[理学—无机化学]