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1. 内蒙古大学 化学化工学院
2. 北京大学 稀土材料及应用重点实验室
收稿:2009-08-25,
修回:2009-10-14,
网络首发:2010-11-22,
纸质出版:2010-11-22
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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:
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
&
middot;6H
2
O(1)、Eu
LL
'
1.5
&
middot;2H
2
O(2)、Eu
0.5
Y
0.5
LL
'
1.5
&
middot;3H
2
O(3)、Eu
0.5
La
0.5
LL
'
1.5
&
middot;3H
2
O(4)、Eu
0.5
Gd
0.5
LL
'
1.5
&
middot;3H
2
O(5)、EuZn
L
Cl
2
(C
2
H
5
OH)
2
&
middot;2H
2
O(6)、EuCd
L
Cl
2
-(C
2
H
5
OH)
2.5
&
middot;2H
2
O(7)、EuMn
L
Cl
2
(C
2
H
5
OH)
2
&
middot;2H
2
O(8)、EuNi
L
Cl
2
(C
2
H
5
OH)
2
&
middot;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
&
middot;2H
2
O(2)的荧光强度明显高于二元配合物Eu
L
&
middot;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。
paper
De Silva C R, Wang R Y, Zheng Z P. Highly luminescent Eu(Ⅲ) complexes with 2,4,6-tri(2-pyridyl)-1,3,5-triazine ligand: Synthesis, structural characterization, and photoluminescence studies [J]. Polyhedron, 2006, 25 (17):3449-3455.[2] Sabbatini N, Guardigli N, Lehn J M. Luminescent lanthanide complexes as photochemical supramolecular devices [J]. Coord. Chem. Rev., 1993, 123 (1-2):201-228.[3] Khreis O M, Curry R J, Somertom M, et al. Infrared organic light emitting devices using neodymium tris-(8-hydro oxyquoline) [J]. J. Appl. Phys., 2000, 88 (1):777-780.[4] Yang Hong, Cai Lihua. Studies on the spectra of rare earth dinuclear complexes with o-phenanthroline hydrate [J]. Chin. J. Spectroscopy Laboratory (光谱实验室), 2003, 20 (1):18-20 (in Chinese).[5] Zhang Renjie, Yang Kongzhang. Fluorescence character of rare earth complex with high efficient green light in ordered molecular films [J]. Longmuir, 1997, 13 (26):7141-7145.[6] Ishizaka T, Tero-Kubota S, Kurokawa Y. EPR studies on defects in sol-gel derived alumina films [J]. J. Phys. Chem. Solids, 2003, 64 (5):801-806.[7] Wu Renqimuge, Zhao Yongliang, Wei Xiaoyan, et al. Synthesis, characterization and fluorescence properties of the solid complexes of rare earth with trimesic acid and 1,10-phenanthroline [J]. China Rare Earths (稀土), 2009, 30 (2):1-4 (in Chinese).[8] Zhang Mei, Zhao Yongliang, Zhao Yanfang, et al. Studies on fluorescence property of Eu3+ dinuclear complexes with 2-thiopheneacetic acid and o-phenanthroline [J]. Chin. J. Lumin. (发光学报), 2008, 29 (5):827-832 (in Chinese).[9] Manhass B S, Trikha A K. The relationship between the direction of shifts in carbon-oxygen stretching frequencies of carboxylate complexes and the type of carboxylate coordination [J]. J. India. Chem. Soc., 1982, 6 :315-319.[10] Zhao Yongliang, Zhao Fengying. Study on infrared and fluorescence spectra of Eu(La) complexes with o-phenanthroline and p-phthalic acid [J]. J. Chin. Rare Earth Society (中国稀土学报), 2001, 19 (5):398-401 (in Chinese).[11] Wang Liufang, Wu Jigui, Peng Zhouren, et al. Study on ternary complexes of rare earth elements Ⅳ. Syntheses and properties of ternary complexes of rare earth elements with 3,5-dinitrosalicylic acid and phenanthroline [J]. Chinese Journal of Inorganic Chemistry (无机化学学报), 1990, 48 (2):141-146 (in Chinese).[12] Wei Xiaoyan, Zhao Yongliang, Xue Zhen, et al. Synthesis, characterization and fluorescence property of Dy3+ with halobenzoic acid and nitrogen-heterocyclic complexes [J]. Chin. J. Lumin. (发光学报), 2009, 30 (1):108-112 (in Chinese).[13] Zhao Yongliang, Zhao Fengying, Xue Zhen, et al. Infrared spectra and luminescent properties of p-tert-butylcalic[8] arene-DMF complexes of rare earth nitrates [J]. Chin. J. Lumin. (发光学报), 2006, 27 (3):358-362 (in Chinese).
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