| 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 |
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| 引用本文： | 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). |
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| 作者姓名： | 石晓燕 李文先 秦彩花 郭磊 孙晓军 孙雪莲 耿刚强 |
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| 作者单位： | 内蒙古大学,化学化工学院,内蒙古,呼和浩特,010021 |
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| 基金项目： | 内蒙教育厅科学基金，内蒙古大学513人才基金 |
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| 摘 要： | 合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的四种四元配合物。经元素分析、稀土络合滴定、摩尔电导率及差热-热重分析,表明四元配合物组成为REL5L′(ClO4)] (ClO4) (RE= La,Pr,Nd,Eu;L=C6H5SOC6H5,L′=C6H5COO-)。在红外光谱中,第一配体二苯基亚砜的νS O的特征吸收峰出现在1 037cm-1处,而各稀土配合物的νS O向低波数移动到984 ～989 cm-1,红移50 cm-1左右,表明稀土离子与亚砜基团的氧原子之间发生配位作用。第二配体苯甲酸钠的反对称伸缩振动吸收峰νas(COO -)出现在1 550 cm-1,对称伸缩振动吸收峰νs(COO -)出现在1 416 cm-1处,羧基伸缩振动吸收频率差Δnνas(COO -)-νs(COO -)]值为134cm-1;在所有配合物的红外光谱图中νas(COO -)向高波数方向发生了位移,而νs(COO -)向低波数方向发生了位移,并且Δn值均大于钠盐的Δn值,由此可以认为配合物中羧基是通过单齿方式与稀土离子配位。测定了配合物在丙酮溶液中的摩尔电导率,根据配合物在常见有机溶剂中的摩尔电导率与正负离子的关系结合配合物的红外光谱中高氯酸根离子的四条特征吸收带,表明配合物为1:1型电解质,两个ClO4-无机抗衡阴离子,其中一个在外界,一个进入内界与稀土离子配位。配合物的荧光发射光谱表明,四元配合物的荧光强度比二苯基亚砜高氯酸稀土二元配合物的荧光强度提高469%。磷光光谱表明苯甲酸三重态能级的下限和二苯亚砜三重态能级的上限重叠,导致三重态能级范围扩大,由此可见第二配体的加入提高了配体的三重态能级与Eu3 离子5D0能级的匹配程度。同时在配合物的荧光发射光谱中还可以看到铕离子的电偶极跃迁强度大于磁偶极跃迁,表明稀土离子不处于晶体场的对称中心。在四元配合物中,由于第二配体的加入,往往会降低配合物的对称性,从而增强稀土离子的荧光强度。本文合成的稀土配合物具有良好的荧光性能,而且在室温下稳定,溶解性好,分解温度较高。
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| 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 |
Synthesis and Characterization of Quaternary Complexes of Light Rare Earth Perchlorate with Diphenyl Sulfoxide, Benzoic Acid and Studies on Fluorescence of Eu3+Complex |
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| SHI Xiao-yan,LI Wen-xian,QIN Cai-hua,GUO Lei,SUN Xiao-jun,SUN Xue-lian,GENG Gang-qiang.Synthesis and Characterization of Quaternary Complexes of Light Rare Earth Perchlorate with Diphenyl Sulfoxide, Benzoic Acid and Studies on Fluorescence of Eu3+Complex[J].Chinese Journal of Luminescence,2008,29(5). |
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| Authors: | SHI Xiao-yan LI Wen-xian QIN Cai-hua GUO Lei SUN Xiao-jun SUN Xue-lian GENG Gang-qiang |
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| 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 Δnνas(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 Δnνas(COO-)-νs(COO-)] in complexes is higher than that of Δnνas(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. |
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| Keywords: | light rare earth quaternary complexes diphenyl sulfoxide benzoic acid fluorescence phosphorescent spectra |
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