稀土-间苯二甲酸-乙酰丙酮三元配合物的合成及发光性能  

Synthesis and Luminescent Property of Rare Earth Complexes Constructed by Isophthalic Acid and Acetylacetone

作　　者：鲁雅 胡未极[2] 梁刚锋[1] 赵国良[1,2] LU Ya;HU Weiji;LIANG Gangfeng;ZHAO Guoliang(Zhejiang Normal University Xingzhi College,Jinhua 321004,Zhejiang,China;College of Chemistry and Life Science,Zhejiang Normal University,Jinhua 321004,Zhejiang,China)

机构地区：[1]浙江师范大学行知学院,浙江金华321004 [2]浙江师范大学化学与生命科学学院,浙江金华321004

出　　处：《硅酸盐学报》2021年第4期769-776,共8页Journal of The Chinese Ceramic Society

基　　金：浙江省自然科学基金面上项目(LY12B01003)资助。

摘　　要：在乙醇体系中,由双配体间苯二甲酸(H_(2)PIA)和乙酰丙酮(Hacac)与稀土硝酸盐反应合成了相应的4种稀土三元配合物[Ln_(2)(PIA)_(2)(acac)_(2)](Ln=Sm(1),Eu(2),Tb(3),Dy(4)),用元素分析、红外光谱、热重分析进行表征,并推断了其可能的结构.为便于比较三元配合物的发光性能,同时也制备了相应的稀土间苯二甲酸[Ln2(PIA)3(H_(2)O)_(4)]和稀土乙酰丙酮二元配合物[Ln(acac)_(3)(H_(2)O)].室温下,测定了三元和二元配合物的荧光光谱,结果表明,所有配合物均显示稀土中心离子特有的发射,三元配合物的发光强度好于二元配合物(除了镝配合物),说明双配体对中心离子有协同敏化作用,其实验结果用配体最低三重态能级T_(1)(来自Gauss理论计算)与中心金属离子最低激发态能级的匹配情况予以解释.Four ternary complexes[Ln_(2)(PIA)_(2)(acac)_(2)](Ln=Sm(1),Eu(2),Tb(3),Dy(4))were synthesized with isophthalic acid(H2PIA,C8H604),acetylacetone(Hacac,C5H802)and Ln(NO_(3))_(3)·H_(2)0 in ethanol solution.These complexes were characterized by elemental analysis,infrared(IR)spectra,and thermogravimetric analysis(TG).Their possible structures were proposed.In order to compare the luminescent properties between ternary complexes and corresponding binary complexes,the binary complexes[Ln_(2)(PIA)_(3)(H_(2)O)_(4)]and Ln(acac)_(3)(H_(2)O)(Ln=Sm,Eu,Tb,Dy)were also prepared.The fluorescent spectra of the ternary and binary complexes were determined at room temperature.The results show that all complexes displayed the characteristic emissions of rare earth center ions.The luminescent intensities of the ternary complexes(except the dysprosium complex)were stronger than that of the binary complexes,indicating that the synergistic sensitization effect had occurred for the center ions from the double ligands.These experimental results can be explained by the energy matching of the lowest triplet energy level T_(1)of the two ligands(calculated from Gaussian theory)and the lowest excited state energy level of the central metal ions.

关 键 词：稀土配合物 间苯二甲酸 乙酰丙酮 荧光光谱 

分 类 号：O614.33[理学—无机化学]