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均苯三甲酸铕掺杂配合物的合成及其荧光性能
Synthesis and Fluorescence Properties of Doped Europium Benzene-1 ,3 ,5-tricarboxylate Complexes
- 发光学报 2010年31卷第6期 页码：920-925
- 作者机构：
1. 内蒙古大学 化学化工学院,内蒙古 呼和浩特,010021
2. 北京大学 稀土材料及应用重点实验室 北京,100871
- 作者简介：
- 基金信息：国家自然科学基金(20461002)();内蒙古自然科学基金(200711020203)资助项目()
DOI：
中图分类号： O482.31收稿日期：2009-08-25，
修回日期：2009-10-14，
网络出版日期：2010-11-22，
纸质出版日期：2010-11-22
- 稿件说明：
移动端阅览
马瑞军, 赵永亮, 乌仁其木格, 李欣, 孙慧娟. 均苯三甲酸铕掺杂配合物的合成及其荧光性能[J]. 发光学报, 2010,31(6): 920-925
MA Rui-jun, ZHAO Yong-liang, Wuren Qimuge, LI Xin, SUN Hui-juan. Synthesis and Fluorescence Properties of Doped Europium Benzene-1 ,3 ,5-tricarboxylate Complexes[J]. Chinese Journal of Luminescence, 2010,31(6): 920-925
马瑞军, 赵永亮, 乌仁其木格, 李欣, 孙慧娟. 均苯三甲酸铕掺杂配合物的合成及其荧光性能[J]. 发光学报, 2010,31(6): 920-925 DOI：
MA Rui-jun, ZHAO Yong-liang, Wuren Qimuge, LI Xin, SUN Hui-juan. Synthesis and Fluorescence Properties of Doped Europium Benzene-1 ,3 ,5-tricarboxylate Complexes[J]. Chinese Journal of Luminescence, 2010,31(6): 920-925 DOI：
摘要
合成了两个系列的均苯三甲酸铕配合物。其一是以均苯三甲酸(H
3
btc)为配体
Eu
3+
及掺杂过渡金属Zn
2+
、Cd
2+
、Mn
2+
、Ni
2+
为中心离子的配合物;其二是以均苯三甲酸、邻菲啰啉(Phen)为配体
Eu
3+
及掺杂Y
3+
、La
3+
、Gd
3+
为中心离子的异核稀土配合物。对配合物进行了元素分析、差热-热重、红外光谱、紫外光谱、荧光寿命及荧光性能等方面的测试分析。配合物的组成分别为:Eu
L
6H
2
O(1)、Eu
LL
'
1.5
2H
2
O(2)、Eu
0.5
Y
0.5
LL
'
1.5
3H
2
O(3)、Eu
0.5
La
0.5
LL
'
1.5
3H
2
O(4)、Eu
0.5
Gd
0.5
LL
'
1.5
3H
2
O(5)、EuZn
L
Cl
2
(C
2
H
5
OH)
2
2H
2
O(6)、EuCd
L
Cl
2
-(C
2
H
5
OH)
2.5
2H
2
O(7)、EuMn
L
Cl
2
(C
2
H
5
OH)
2
2H
2
O(8)、EuNi
L
Cl
2
(C
2
H
5
OH)
2
2H
2
O(9)(其中
L
=btc
L
'=Phen)。均苯三甲酸的羧酸氧原子和邻菲啰啉的氮原子与稀土离子配位。差热-热重的测试结果表明
均苯三甲酸-邻菲啰啉异核稀土配合物的分解温度为490℃
铕掺杂过渡金属配合物分解温度为450℃
两类配合物的最终分解产物均为氧化物。荧光光谱的测试结果表明
三元配合物Eu
LL
'
1.5
2H
2
O(2)的荧光强度明显高于二元配合物Eu
L
2H
2
O(1);配合物(3)、(4)、(6)、(7)中
Y
3+
、La
3+
、Zn
2+
、Cd
2+
无未充满的d层或f层电子
对Eu
3+
的荧光有增强作用;配合物(5)中的Gd
3+
有4f
7
半充满稳定电子层结构
对Eu
3+
的荧光也有增强作用。在配合物(8)和(9)中
Mn
2+
和Ni
2+
的未充满d层电子消耗配体吸收的能量
对Eu
3+
的荧光有猝灭作用。
Abstract
Nine doped europium benzene-1
3
5-tricarboxylate complexes have been synthesized and characterized. Elemental analysis
rare earth coordination titration
IR spectra
UV absorption spectra and TG-DTA were used to characterized these complexes. The studies of the fluorescence spectra and lifetimes of the nine complexes show obviously difference. Compared with binary complex of Eu
L
6H
2
O(1)
the ternary complex Eu
LL
'
1.5
2H
2
O exhibits stronger luminescence intensity. This result indicates that the fluorescence intensities of the complexes depend on ligands. In the binary complex the ligand (btc) transfers some energy to Eu
3+
but in ternary complexes both the ligands (btc and phen) transfer more energy. The fluorescence peak positions of the other seven are similar to (1) and (2)
but the luminescence intensities of these complexes are obviously different. The positions of Eu
3+
emission peak of the complexes do not change
indicating that the introduction of doped rare earth ions or transition-metal ions does not influence the energy level of Eu
3+
in the complexes. The dinuclear complexes
which contain the metal ions Y
3+
La
3+
Zn
2+
and Cd
2+
without unsa-turated d-layer or f-layer electrons
display sensitization and strengthening to fluorescence properties of those complexes
respectively. Therefore
the energy absorption by organic ligands will not be consumed by the d-d or f-f transfer. In this manner
Eu
3+
absorbs much more energy through intramolecular energy transfer and luminous intensity is enhanced. Gd
3+
has inert half-full 4f
7
electronic configuration
so the luminous intensity of (5) is also strong and similar with (3) and (4). Complexes (8) and (9)
containing Mn
2+
and Ni
2+
respectively
exhibit fluorescence quenching
which is caused by the unsaturated d-layer electrons consuming the energy in the form of radiative transition.
关键词
Keywords
references
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