发光学报2008，Vol.29Issue(5)：772-778,7.
二苯基亚砜、苯甲酸与轻稀土高氯酸四元配合物的合成表征及光致发光
Synthesis and Characterization of Quaternary Complexes of Light Rare Earth Perchlorate with Diphenyl Sulfoxide, Benzoic Acid and Studies on Fluorescence of Eu3+Complex
摘要
Abstract
Four solid quaternary complexes of light rare earth perchlorate with diphenyl sulfoxide (L) and benzoic acid (L′) have been synthesized and characterized. By elemental analysis, TGA-DTA and the molar conductivities in acetone solution studies,the composition of the complexes were suggested as [REL5L′(ClO4)](ClO4) (RE= La,r,d,u;L=C6H5SOC6H5,L′=C6H5COO-). As shown in IR spectra,the absorption band associated with the SO stretching modes in the first ligand diphenyl sulfoxide appears at 1 037 cm-1,while the absorption bands in the complexes appear between 987 cm-1 and 989 cm-1. A shift of the SO stretching frequency towards lower wave number by about 50 cm-1 suggests that rare earth ions are bonded with an oxygen atom in sulfoxyl group. In the second ligand benzoate,he absorption band associated with νas(COO-) appears at 1 550 cm-1,νs(COO-) appears at 1 416 cm-1. The value of Δn[νas(COO-)-νs(COO-)] is 134 cm-1. A shift of νas(COO-) frequency in complexes towards higher wave number,while a shift of νs(COO-) frequency in complexes towards lower wave number. What's more,the value of Δn[νas(COO-)-νs(COO-)] in complexes is higher than that of Δn[νas(COO-)-νs(COO-)] in sodium benzoate. This showed that benzoate (L′) bonded with RE3+ ions by one oxygen atom in carboxyl group which coordinate as an unidentate group. One of two perchlorates (ClO-4) is coordinated with RE3+ while another is not. Fluorescent spectra of Eu3+ complex showed that quaternary complexes have stronger fluorescence than the binary one whose ligand is diphenyl sulfoxide,(the fluorescence intensity of Eu3+ complex increased by 469%). Phosphorescent spectra of two ligands showed that the lower limit of the triplet state with benzoic acid was overlapped by the upper limit with diphenyl sulfoxide,the energy level range of triplet state was extended. As a result,matching extent of triplet state of ligands with excited state of the rare earths have been increased by coordination of the second ligand benzoic acid,the transmit efficiency also have been increased. Attributed to the addition of the second ligand,the symmetry of the complexes always have been decreased,as a result,the fluorescence intensity was increased.关键词
二苯基亚砜/苯甲酸/轻稀土四元配合物/磷光光谱/发光Key words
light rare earth quaternary complexes/diphenyl sulfoxide/benzoic acid/fluorescence/phosphorescent spectra分类
数理科学引用本文复制引用
石晓燕,李文先,秦彩花,郭磊,孙晓军,孙雪莲,耿刚强..二苯基亚砜、苯甲酸与轻稀土高氯酸四元配合物的合成表征及光致发光[J].发光学报,2008,29(5):772-778,7.基金项目
内蒙教育厅科学基金(NJ 06047) （NJ 06047）
内蒙古大学"513"人才基金(205150)资助项目 The Education Department of inner mongolia science foundation(NJ06047) （205150）
Inner Mongolia University"513"Second Administrative Levels person with Ability Foundation Project(205150) （205150）
