镧、钆掺杂铕三元荧光配合物的合成及性能研究
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摘要
稀土发光配合物的研究是无机发光、有机发光和生物发光研究的交叉学科,此类发光材料被广泛应用于各种高新技术领域。本论文以廉价的非荧光稀土离子镧或钆(不同比例)掺杂铕作为中心离子,价廉易得的芳香羧酸(间氯苯甲酸、对甲基苯甲酸、大茴香酸、对羟基苯甲酸、苯甲酸)和1.10-菲咯啉为第一配体,油酸和十一烯酸为第二配体,在最优工艺条件下合成了108个新的红色荧光配合物。通过元素分析和EDTA配位滴定分析确定了它们的组成;通过紫外光谱分析和红外光谱分析对它们的结构进行了表征;采用热分析仪研究了它们的热稳定性能;通过荧光光谱分析研究了它们的荧光性能,并得出了如下结果:
1、镧、钆掺杂铕配合物的荧光强度与配体分子结构和配合物结构有关。掺杂相同量镧的配合物Eu_kLa_(1-k)(X)_2(UA)·3H_2O中配体向稀土离子Eu~(3+)传递能量的顺序为:对甲苯甲酸>间氯苯甲酸>苯甲酸>大茴香酸>1.10-菲咯啉>对羟基苯甲酸;掺杂相同量钆的配合物EukGd1-k(X)2(UA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:间氯苯甲酸>1.10-菲咯啉>大茴香酸>对甲苯甲酸>苯甲酸>对羟基苯甲酸;掺杂相同量镧的配合物EukLa1-k(X)2(OA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:对甲苯甲酸>1.10-菲咯啉>苯甲酸>大茴香酸>间氯苯甲酸啉>对羟基苯甲酸;掺杂相同量钆的配合物EukGd1-k(X)2(OA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:1.10-菲咯啉>对甲苯甲酸>大茴香酸>间氯苯甲酸>苯甲酸>对羟基苯甲酸。
2、非荧光离子La3+、Gd3+的掺杂对Eu~(3+)配合物的荧光发射有增强作用。随着Gd3+、La3+掺杂量的增加,铕配合物的荧光强度增强。非荧光离子La3+、Gd3+对Eu~(3+)的敏化作用表现为:先随掺杂量的增加而增强,而后逐渐降低的共同特性。掺杂不同比例镧、钆的铕配合物,其荧光强度的基本大小顺序为:掺杂50%,掺杂75%,掺杂25%,掺杂100%。
3、镧或钆掺杂铕芳香羧酸十一烯酸配合物的热稳定性强弱顺序为:Eu_(0.5)Y_(0.5)(MCBA)_2(UA)·3H_2O>Eu_(0.5)Y_(0.5)(BA)_2(UA)·3H_2O>Eu0.5Y0.5(PHBA)2 (UA)·3H2O>Eu0.5Y0.5(MBA)2(UA)·3H2O>Eu0.5Y0.5(PMBA)2(UA)·3H2O>Eu0.5Y0.5(Phen) (UA)3·H2O ;镧或钆掺杂铕芳香羧酸油酸配合物的热稳定性强弱顺序为:Eu_(0.5)Y_(0.5)(MCBA)_2(OA)·3H_2O>Eu0.5Y0.5(PHBA)2(OA)·3H2O>Eu0.5Y0.5(BA)2 (OA)·3H2O>Eu0.5Y0.5(PMBA)2(OA)·3H2O>Eu0.5Y0.5(Phen)(UA)3·H2O>Eu0.5Y0.5(MBA)2 (UA)·3H2O。
4、La3+、Gd3+以不同比例掺杂Eu~(3+)配合物,在紫外光的激发下,Eu~(3+)荧光发射峰位置只有微小变化,但对其荧光发射强度影响较大。随着掺杂离子含量的增
The research of the rare earth luminescent complexes is belong to the cross field of inorganic, organic and biological luminescence research. This kind of luminnescent material has widely been applied to many high-tech areas. In this dissertation, one hundred and eight new red fluorescence complexes of europium adulterated by cheap non- fluorescence lanthanum or gadolinium with the first ligands of the cheap and popular aromatic carboxylic acid (m-chlorobenzoic acid, p-methylbenzoic acid, methoxybenzoic acid, p-hydroxylbenzoic acid, benzoic acid) and 1,10-phenanthroline, and the second ligands of oleic acid and undecenoic acid have been synthesized under the best optimisation synthesis conditions. Their molecular compositions and structures were characterized by means of elemental analysis, EDTA titrimetric method, FT-IR and UV spectroscopies; their thermal properties were studied by thermal analysis instrument; Their luminescent properties were investigated by means of fluorescence instrument. The main results are as follows:
1. The fluorescence intensity of the complexes of europium adulterated by lanthanum or gadolinium has relationships with the structure of ligands and complexes. The ability order of the first ligand transferring light energy to the central europium ion was that of p-methylbenzoic acid > m-chlorobenzoic acid > benzoic acid > methoxybenzoic acid > 1,10-phenanthroline > p-hydroxylbenzoic acid in the Eu_kLa_(1-k)(X)_2(UA)·3H_2O. The ability order of the first ligand transferring light energy to the central europium ion was that of m-chlorobenzoic acid > 1,10-phenanthroline > methoxybenzoic acid > p-methylbenzoic acid > benzoic acid > p-hydroxylbenzoic acid in the EukGd1-k(X)2(UA)·3H2O. The ability order of the first ligand transferring light energy to the central europium ion was that of p-methylbenzoic acid > 1,10-phenanthroline > benzoic acid > methoxybenzoic acid > m-chlorobenzoic acid > p-hydroxylbenzoic acid in the EukLa1-k(X)2(OA)·3H2O. The ability order of the first ligand transferring light energy to the central europium ion was that of 1,10-phenanthroline > p-methylbenzoic acid > methoxybenzoic acid > m-chlorobenzoic acid > benzoic acid > p-hydroxylbenzoic acid in the EukGd1-k(X)2(OA)·3H2O.
2. The adulteration of the non- fluorescence lanthanum or gadolinium ions can enhance the fluorescence intensity of the complexes of europium,but only have little influence on the locations of the fluorescence characteristic peaks. The fluorescence intensity of the complexes of europium increased with the increment of adulteration
1、镧、钆掺杂铕配合物的荧光强度与配体分子结构和配合物结构有关。掺杂相同量镧的配合物Eu_kLa_(1-k)(X)_2(UA)·3H_2O中配体向稀土离子Eu~(3+)传递能量的顺序为:对甲苯甲酸>间氯苯甲酸>苯甲酸>大茴香酸>1.10-菲咯啉>对羟基苯甲酸;掺杂相同量钆的配合物EukGd1-k(X)2(UA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:间氯苯甲酸>1.10-菲咯啉>大茴香酸>对甲苯甲酸>苯甲酸>对羟基苯甲酸;掺杂相同量镧的配合物EukLa1-k(X)2(OA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:对甲苯甲酸>1.10-菲咯啉>苯甲酸>大茴香酸>间氯苯甲酸啉>对羟基苯甲酸;掺杂相同量钆的配合物EukGd1-k(X)2(OA)·3H2O中配体向稀土离子Eu~(3+)传递能量的顺序为:1.10-菲咯啉>对甲苯甲酸>大茴香酸>间氯苯甲酸>苯甲酸>对羟基苯甲酸。
2、非荧光离子La3+、Gd3+的掺杂对Eu~(3+)配合物的荧光发射有增强作用。随着Gd3+、La3+掺杂量的增加,铕配合物的荧光强度增强。非荧光离子La3+、Gd3+对Eu~(3+)的敏化作用表现为:先随掺杂量的增加而增强,而后逐渐降低的共同特性。掺杂不同比例镧、钆的铕配合物,其荧光强度的基本大小顺序为:掺杂50%,掺杂75%,掺杂25%,掺杂100%。
3、镧或钆掺杂铕芳香羧酸十一烯酸配合物的热稳定性强弱顺序为:Eu_(0.5)Y_(0.5)(MCBA)_2(UA)·3H_2O>Eu_(0.5)Y_(0.5)(BA)_2(UA)·3H_2O>Eu0.5Y0.5(PHBA)2 (UA)·3H2O>Eu0.5Y0.5(MBA)2(UA)·3H2O>Eu0.5Y0.5(PMBA)2(UA)·3H2O>Eu0.5Y0.5(Phen) (UA)3·H2O ;镧或钆掺杂铕芳香羧酸油酸配合物的热稳定性强弱顺序为:Eu_(0.5)Y_(0.5)(MCBA)_2(OA)·3H_2O>Eu0.5Y0.5(PHBA)2(OA)·3H2O>Eu0.5Y0.5(BA)2 (OA)·3H2O>Eu0.5Y0.5(PMBA)2(OA)·3H2O>Eu0.5Y0.5(Phen)(UA)3·H2O>Eu0.5Y0.5(MBA)2 (UA)·3H2O。
4、La3+、Gd3+以不同比例掺杂Eu~(3+)配合物,在紫外光的激发下,Eu~(3+)荧光发射峰位置只有微小变化,但对其荧光发射强度影响较大。随着掺杂离子含量的增
The research of the rare earth luminescent complexes is belong to the cross field of inorganic, organic and biological luminescence research. This kind of luminnescent material has widely been applied to many high-tech areas. In this dissertation, one hundred and eight new red fluorescence complexes of europium adulterated by cheap non- fluorescence lanthanum or gadolinium with the first ligands of the cheap and popular aromatic carboxylic acid (m-chlorobenzoic acid, p-methylbenzoic acid, methoxybenzoic acid, p-hydroxylbenzoic acid, benzoic acid) and 1,10-phenanthroline, and the second ligands of oleic acid and undecenoic acid have been synthesized under the best optimisation synthesis conditions. Their molecular compositions and structures were characterized by means of elemental analysis, EDTA titrimetric method, FT-IR and UV spectroscopies; their thermal properties were studied by thermal analysis instrument; Their luminescent properties were investigated by means of fluorescence instrument. The main results are as follows:
1. The fluorescence intensity of the complexes of europium adulterated by lanthanum or gadolinium has relationships with the structure of ligands and complexes. The ability order of the first ligand transferring light energy to the central europium ion was that of p-methylbenzoic acid > m-chlorobenzoic acid > benzoic acid > methoxybenzoic acid > 1,10-phenanthroline > p-hydroxylbenzoic acid in the Eu_kLa_(1-k)(X)_2(UA)·3H_2O. The ability order of the first ligand transferring light energy to the central europium ion was that of m-chlorobenzoic acid > 1,10-phenanthroline > methoxybenzoic acid > p-methylbenzoic acid > benzoic acid > p-hydroxylbenzoic acid in the EukGd1-k(X)2(UA)·3H2O. The ability order of the first ligand transferring light energy to the central europium ion was that of p-methylbenzoic acid > 1,10-phenanthroline > benzoic acid > methoxybenzoic acid > m-chlorobenzoic acid > p-hydroxylbenzoic acid in the EukLa1-k(X)2(OA)·3H2O. The ability order of the first ligand transferring light energy to the central europium ion was that of 1,10-phenanthroline > p-methylbenzoic acid > methoxybenzoic acid > m-chlorobenzoic acid > benzoic acid > p-hydroxylbenzoic acid in the EukGd1-k(X)2(OA)·3H2O.
2. The adulteration of the non- fluorescence lanthanum or gadolinium ions can enhance the fluorescence intensity of the complexes of europium,but only have little influence on the locations of the fluorescence characteristic peaks. The fluorescence intensity of the complexes of europium increased with the increment of adulteration
引文
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