由对羟基苯乙酸与乙酰丙酮共同构筑的稀土三元配合物的合成及荧光性质  

Synthesis,Luminescent Properties of Rare Earth Complexes Based on p-Hydroxyphenylacetic Acid and Acetylacetone

作　　者：鲁雅 胡未极[2] 赵国良[1,2] Lu Ya;Hu Weiji;Zhao Guoliang(Zhejiang Normal University Xingzhi College,Zhejiang 321004,China;College of Chemistry and Life Science,Zhejiang Normal University,Zhejiang 321004,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：《中国稀土学报》2021年第2期264-274,I0003,共12页Journal of the Chinese Society of Rare Earths

基　　金：浙江省自然科学基金项目(LY12B01003)资助。

摘　　要：以对羟基苯乙酸(H_(2)PPA,C_(8)H_(8)O_(3))和乙酰丙酮(Hacac,C_(5)H_(8)O_(2))为配体,稀土硝酸盐为金属源,用溶液法合成了4个稀土配合物[Ln_(2)(HPPA)(acac)_(4)(NO_(3))(H_(2)O)_(2)]n(Ln=Sm,(1);Eu,(2);Tb,(3);Dy,(4))。产物为异质同晶,铕配合物为单晶样,其余为多晶粉末。通过元素分析、红外光谱、热重分析、X射线单晶衍射、X射线粉末衍射等方法对该系列配合物进行了表征。室温下分别测定了三元配合物在可见区的荧光光谱和荧光寿命。为探究对羟基苯乙酸和乙酰丙酮双配体对稀土中心离子荧光强度的影响,分别合成了单一对羟基苯乙酸系列稀土配合物和单一乙酰丙酮系列稀土配合物,并测定了这两个系列稀土配合物的荧光光谱。实验结果表明:三个系列配合物均显示稀土中心离子的特征发光,同一稀土离子三元配合物的发光强度好于二元配合物,说明双配体对中心离子有协同作用。通过使用Gaussian 09量子化学程序包计算了对羟基苯乙酸和乙酰丙酮最低激发三重态(T_(1))能级,并与稀土离子最低激发态能级的匹配程度进行分析,解释了双配体与单一配体对稀土中心离子荧光强度的影响。Four ternary complexes[Ln_(2)(HPPA)(acac)_(4)(NO_(3))(H_(2)O)_(2)]n(Ln=Sm,(1);Eu,(2);Tb,(3);Dy,(4))were synthesized by p-hydroxyphenylacetic acid(H_(2)PPA,C_(8)H_(8)O_(3)),acetylacetone(Hacac,C5H8O2)and Ln(NO_(3))_(3)·nH_(2)O in ethanol solution.They were characterized by elemental analysis,IR spectra,TG,PXRD and single crystal X-ray diffraction method.The products are heterogeneous isomorphous,the europium complex is single crystal and the rest are polycrystalline powder.In addition,the fluorescence spectra and fluorescence lifetimes of the ternary complexes in the visible region were measured at room temperature.In order to investigate the effect of p-hydroxyphenylacetic acid and acetylacetone bis-ligands on the fluorescence intensity of rare earth center ions,a single p-hydroxyphenylacetic acid series rare earth complexes and a single acetylacetone series rare earth complexes were synthesized,and their fluorescence spectra were also determined.The experimental results showed that the three series of complexes display the characteristic luminescence of the rare earth center ions,the luminescence intensity of ternary complex is better than that of the binary complexes for the same rare earth ion,indicating that the double ligands have a synergistic effect on the central ions.The lowest excited triplet(T1)energy level of p-hydroxyphenylacetic acid and acetylacetone were calculated by using the Gaussian 09 quantum chemistry package,and the degree of matching with the lowest excited state energy level of rare earth ions were analyzed,explaining the effect of fluorescence intensities of the rare earth center ions by double ligands and single ligand.

关 键 词：稀土 对羟基苯乙酸 乙酰丙酮 配合物 荧光 

分 类 号：O641[理学—物理化学]