二苯基亚砜、苯甲酸与重稀土高氯酸四元配合物的合成及Tb^(3+)、Dy^(3+)光致发光  

Synthesis of Complexes of Rare Earth Perchlorate with Diphenyl Sulfoxide and Benzoic Acid and Fluorescence of Tb^(3+) and Dy^(3+)

作　　者：李文先[1] 秦彩花[1] 石晓燕[1] 耿刚强[1] 孙晓军[1] 孙雪莲[1] 柴文娟[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：《稀土》2009年第4期6-11,共6页Chinese Rare Earths

基　　金：国家自然科学基金项目资助(20861005);内蒙古高等学校科学基金资助(NJ06047);内蒙古大学"513"二层次人才基金资助(205150)

摘　　要：合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的六种四元配合物。经元素分析、差热-热重分析,表明四元配合物组成为[REL5L′(ClO4)](ClO4)(RE=Tb,Dy,Ho,Er,Tm,Yb;L=C6H5SOC6H5,L′=C6H5COO-)。IR、1HNMR表明,第一配体二苯基亚砜通过一个亚砜基氧原子、第二配体苯甲酸脱质子以阴离子形式通过一个羧基氧原子单齿与稀土离子配位。摩尔电导率表明配合物为1∶1型,两个ClO4-无机抗衡阴离子,其中一个在内界,一个在外界;配合物的荧光光谱表明,Tb3+、Dy3+四元配合物的荧光强度分别比二苯基亚砜与高氯酸稀土二元配合物的荧光强度提高226%和422%。磷光光谱表明第二配体的加入提高了配体的三重态能级与稀土离子激发态能级的匹配程度。铽配合物的电子顺磁共振谱在g=1.9920处出现一个单峰,表明该配合物具有成单电子,是顺磁性物质。Six solid quaternary complexes of heavy rare earth perchlorate with diphenyl sulfoxide（L） and benzoic acid（L′）have been synthesized and characterized.By elemental analysis,TG-DTA and the molar conductivity measureraents,the composition of the complexes was suggested as [REL5L′（ClO4）]（ClO4）（RE=Tb,Dy,Ho,Er,Tm,Yb;L=C6H5SOC6H5,L′= C6H5COO-）.One of the two perchlorates（ClO4-） is coordinated with RE3＋,while another is not.TG-DTA indicated that the decomposition temperature of the complexes is high,so they are thermostable.IR spectra and 1 HNMR studies indicated that the first ligand diphenyl sulfoxide（L） bonded with RE3＋ by the oxygen atom in sulfinyl group while the second ligand benzoic acid（L′） bonded with RE3＋ ions by one oxygen atom in carboxyl group which coordinate as an unidentate group.Fluorescent spectra of Tb3＋ and Dy3＋ complexes showed that quaternary complexes have the stronger fluorescence than the binary ones whose ligand is diphenyl sulfoxide（the fluorescence intensity of Tb3＋ and Dy3＋ complexes increased by 226% and 422% respectively）.Phosphorescent spectra of two ligands showed that matching extent of triplet state of ligands with excited state of the rare earth have been increased by coordination of second ligand benzoic acid.In addition,there is a peak in the EPR spectrum of [Tb L5L′（ClO4）]（ClO4） at the position of g=1.9920,it indicated that there is single electron in this complex,so the complex is paramagnetic.

关 键 词：二苯基亚砜 苯甲酸 稀土四元配合物 发光 

分 类 号：O482.31[理学—固体物理] O614.33[理学—物理]