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内蒙古大学 化学化工学院, 内蒙古 呼和浩特 010021
收稿日期:2011-05-18,
修回日期:2011-06-12,
网络出版日期:2011-09-22,
纸质出版日期:2011-09-22
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李海燕, 赵永亮, 张雁冰. 2,4,6-三吡啶基三嗪-芳香羧酸镝配合物的合成及其荧光性能[J]. 发光学报, 2011,32(9): 869-873
LI Hai-yan, ZHAO Yong-liang, ZHANG Yan-bing. Synthesis and Fluorescence Properties of Complexes of Dysprosium with 2,4,6-tris-(2-pyridyl)-s-triazine[J]. Chinese Journal of Luminescence, 2011,32(9): 869-873
分别以2
4
6-三吡啶基三嗪(TPTZ)、对羟基苯甲酸和对苯二甲酸为配体
以Dy
3+
为中心合成了不同组成的5种配合物。对其进行了元素分析、紫外光谱、红外光谱、荧光激发和发射光谱的测定。推测配合物的组成分别为: (1)Dy(TPTZ)(NO
3
)
3
(C
2
H
5
OH )H
2
O;(2)Dy(TPTZ)
2
(NO
3
)
3
(C
2
H
5
OH )H
2
O;(3)Dy
2
(TPTZ)(NO
3
)
6
(C
2
H
5
OH )2H
2
O; (4)Dy(TPTZ)(C
7
H
5
O
3
)
3
(C
2
H
5
OH)2H
2
O; (5)Dy
2
(TPTZ)
2
-(C
8
H
4
O
4
)(NO
3
)
4
(C
2
H
5
OH )H
2
O。硝酸根的氧原子、芳香酸的羧基氧和稀土离子配位
TPTZ以主配位点和中配位点的氮原子与稀土离子成键。配合物的形成对配体的共轭-
*
跃迁影响不大。荧光强度测试表明
硝酸根、不同的芳香羧酸作为阴离子配体的镝配合物的发光强度有很大差别。芳香羧酸配体对镝配合物的荧光增强最大
镝离子浓度高
荧光强度也高。配合物(2)荧光强度大于配合物(1)
配合物(3)荧光强度大于配合物(2)
可见配体TPTZ多或者发光离子浓度高则配合物发光强度高;配合物(4)荧光强度强于配合物(1)
表明对羟基苯甲酸吸收和传递光能强于硝酸根;配合物(5)的荧光强度是5个配合物中最高的
表明对苯二甲酸三重态能级与Dy
3+
的最低激发态能级匹配
对光的吸收和传递也好
同时也看出发光的Dy
3+
离子量增加
配合物的发光强度增强。
2
4
6-Tris(2-pyridyl)-1
3
5-triazine
p-hydroxybenzoic acid and p-phthalic acid have been reported as ligands by many researchers recently. And these ligands react with rare earth ions producing the corresponding complexes
which have excellent luminous performances and are expected to be good luminescent materials. In this paper
we firstly reported that the TPTZ ligand reacted with dysprosium ion
produced the corresponding complexes. These complexes were fully characterized with UV
IR and elementary analysis. The composition of these complexes were supposed to be: (1)Dy(TPTZ)(NO
3
)
3
(C
2
H
5
OH)H
2
O; (2)Dy-(TPTZ)
2
(NO
3
)
3
(C
2
H
5
OH)H
2
O; (3)Dy
2
(TPTZ)(NO
3
)
6
(C
2
H
5
OH)2H
2
O;(4)Dy(TPTZ)-(C
7
H
5
O
3
)
3
(C
2
H
5
OH)2H
2
O;(5)Dy
2
(TPTZ)
2
(C
8
H
4
O
4
)(NO
3
)
4
(C
2
H
5
OH)H
2
O. The oxygen atoms of nitrate and carboxyl group from aromatic acids coordinate to dysprosium ion
nitrogen atoms from TPTZ generate bonds with dysprosium ion. The formation of complex has little effect on conjugation bond -
*
electron transition of the ligand. The luminous intensities of dysprosium complexes with different composition are different. The p-phthalic acid complex has the strongest fluorescence intensity. Fluorescence intensity of the complex (2) is stronger than complex (1)
while fluorescence intensity of the complex (3) is stronger than complex (2). It shows that the more TPTZ ligands or dysprosium ions are
the stronger fluorescence intensity is. Fluorescence intensity of the complex (4) is stronger than complex (1).It shows that the p-hydroxybenzoic acid is better at absorption and transmission of light than nitrate. Fluorescence intensity of the complex (5) is the strongest in all the complexes. It shows that p-phthalicacid has the strongest absorption of light
it also shows that when Dy ions at higher concentrations
the fluorescence intensity is also stronger.
Li Ying, Zhao Yongliang. Intramolecular energy transfer and co-luminescence effect in rare earth ions (La, Y, Gd and Tb) d-oped with Eu3+ -diketone complexes [J]. J. Fluoresc., 2009, 19 (4):641-647.[2] Lin Xuemei, Zhao Yongliang, Zhou Yongsheng, et al. Synthesis, characterization and fluorescence properties of complexes terbium with halobenzoic acid and 2,4,6-tris-(2-pyridyl)-s-triazine [J]. Chin. J. Lumin. (发光学报), 2011, 32 (3):220-226 (in Chinese).[3] Zheng Xiangjun, Jin Linpei, Wang Zheming, et al. Structure and photophysical properties of europium complexes of succinamic acid and 1,10-phenanthroline [J]. Polyhedron, 2003, 22 (2):323-330.[4] Ren Xiaoming, Wei Changping, Wang Peng, et al. Preparation and fluorescence properties of ternary complexes of EuBA)3PIP and Eu(BA)3phen [J]. Chin. J. Lumin. (发光学报), 2009, 30 (2):252-256 (in Chinese).[5] Li Wenxian, Shi Xiaoyan, Sun Xiaojun, et al. Enhanced luminescence in (DYx,Tm<em>y) complexes [J]. Chin. J. Lumin. (发光学报), 2009, 30 (5):568-574 (in English).[6] Li H R, Zhang H J, Lin J. Preparation and luminescence properties of ormosil material doped with Eu(TTA)3phen complex [J]. J. Non-Cryst. Solids, 2000, 278 (1-3):218-222.[7] Lu Yongquan, Deng Zhenghua. Practical Infrared Spectroscopy Analysis [M]. Beijing: Electronic Industry Press, 1989:80-167 (in Chinese).[8] Zhao Yongliang, Yang Xiaohua. Study on the infrared and fluorescence of complexes of terbium and yttrium with p-phthalic acid and phenathroline [J]. Spectroscopy and Spectral Analysis (光谱学与光谱分析), 2002, 22 (2):223-225 (in Chinese).[9] Dong Dewen, Men Yongfeng, Jiang Shichun. Preparation and luminescence properties of lanthanide complexes and their si1ica-based composites [J]. Materials Chemistry and Physics, 2001, 70 (1):249-253.[10] Sato S, Wada M. Relation between intramolecular energy transfer efficiencies and triplet state energies in rare earth -diketone chelates [J]. Bull. Chem. Soc. Jpn., 1970, 43 (7):1955-1962.[11] Chen Fangfang, Bian Zuqiang, Huang Chunhui. Progress in electroluminescence based on europium(III)complexes [J]. J. Chin. Rare Earth Society (中国稀土学报), 2007, 25 (4):385-395 (in Chinese).[12] Xue Weixing, Li Jianyu. Synthesis and fluorescent properties of Dy(Ⅲ)complexes with 1,5-bis(1',3'-diphenyl'-5'-pyrazolone-4')-1,5-pentanedione(BDPPPD) [J]. Fine Chem. (精细化工), 2002, 19 (1):22-24 (in Chinese).[13] Zhang Ao, Dong Liming, Jiang Jianxin, et al. La3+ doped Eu3+trimellitic acid ternary phenanthroline synthesis and fluorescence properties [J]. Chin. J. Lumin. (发光学报), 2010, 3l (1):131-136 (in Chinese).[14] 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).[15] Weissman S I. Intramolecular energy transfer-the fluorescence of europium [J]. J.Chem. Phys., 1942, 10 (1): 214-217.[16] Tang B, Jin L P, Zheng X J, et al. Luminescence enhancement of Eu3+ in the Eu3+-dibenzoylmethide-oligomer (styrene-co-acrylic acid) ternary composite [J]. Spectrochim. Acta Part A, 1999, 55 (9):1731-1736.
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