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河北师范大学 化学与材料科学学院,河北 石家庄,050016
收稿日期:2009-11-09,
修回日期:2010-01-05,
网络出版日期:2010-11-22,
纸质出版日期:2010-11-22
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韩华, 杨慧洁, 葛庆莎, 王淑萍, 王瑞芬. 铕、铽四元配合物的合成及其发光性能[J]. 发光学报, 2010,31(6): 908-913
HAN Hua, YANG Hui-jie, GE Qing-sha, WANG Shu-ping, WANG Rui-fen. Synthesis and Fluorscence of Quaternary Europium and Terbium Complexes with Aromatic Carboxylic Acid and 1,10-phenanthroline[J]. Chinese Journal of Luminescence, 2010,31(6): 908-913
韩华, 杨慧洁, 葛庆莎, 王淑萍, 王瑞芬. 铕、铽四元配合物的合成及其发光性能[J]. 发光学报, 2010,31(6): 908-913 DOI:
HAN Hua, YANG Hui-jie, GE Qing-sha, WANG Shu-ping, WANG Rui-fen. Synthesis and Fluorscence of Quaternary Europium and Terbium Complexes with Aromatic Carboxylic Acid and 1,10-phenanthroline[J]. Chinese Journal of Luminescence, 2010,31(6): 908-913 DOI:
以对苯二甲酸(p-PA)、苯甲酸(BA)、邻(间、对)甲基苯甲酸和1
10-邻菲啰啉(phen)为配体
合成了4种Eu(Ⅲ)和4种Tb(Ⅲ)的四元配合物。通过EDTA配位滴定分析和元素分析
确定了各配合物的组成。利用红外光谱分析对配合物的结构进行了初步表征
在配合物中羧基氧原子和1
10-邻菲啰啉中的氮原子均参与了配位。在室温条件下
测定了各固体配合物的激发和发射光谱
结果表明:4种铕的四元配合物中
苯甲酸配合物在614nm最强发射峰的荧光强度强于3种甲基取代苯甲酸配合物的荧光强度;4种铽的四元配合物中
以对甲基苯甲酸为配体的配合物在545nm最佳发射峰和490nm次强发射峰的荧光强度较高。
Rare earth metal complexes have special characteristics
such as extremely narrow emission bands and high internal quantum efficiencies
which are suitable to be used as the emission materials. Eu(Ⅲ) complexes are a kind of good red luminescence materials and Tb(Ⅲ) complexes are a kind of good green luminescence materials. During the past decade
many ternary rare earth complexes have been reported
but quaternary rare earth complexes are seldom reported. In this article
eight quaternary complexes of Eu(Ⅲ) and Tb(Ш) have been synthesized with benzoic acid(BA)
p-phthalic acid(p-PA)
o(m
p)-methylbenzoic acid as the first ligand and the neutral phenanthroline as the second ligand. They were characte-rized by EDTA titration
elemental analysis and IR methods. Their compositions were: Eu
2
(p-PA)(BA)
4
-(phen)
2
2H
2
O
Eu
2
(p-PA)(o-MBA)
4
(phen)
2
2H
2
O
Eu
2
(p-PA)(m-MBA)
4
(phen)
2
2H
2
O
Eu
2
(p-PA)(p-MBA)
4
(phen)
2
H
2
O
Tb
2
(p-PA)(BA)
4
(phen)
2
2H
2
O
Tb
2
(p-PA)(o-MBA)
4
(phen)
2
2H
2
O
Tb
2
(p-PA)(m-MBA)
4
(phen)
2
2H
2
O and Tb
2
(p-PA)(p-MBA)
4
(phen)
2
H
2
O
respectively. In these complexes
the metal ions were bonded to the oxygen atoms of carboxylate and the nitrogen atoms of phen. The excitation and luminescence spectra of the complexes were carried out at room temperature. Four kinds of Eu(Ⅲ) complexes emit intense red fluorescence under ultraviolet excitation. The intensity order of the strongest emission peak
5
D
0
7
F
2
(614 nm) for these Eu(Ⅲ) complexes were: Eu
2
(p-PA)(BA)
4
-(phen)
2
2H
2
O>Eu
2
(p-PA)(o-MBA)
4
(phen)
2
2H
2
O
>
Eu
2
(p-PA)(p-MBA)
4
(phen)
2
H
2
O>Eu
2
(p-PA)(m-MBA)
4
(phen)
2
2H
2
O. Four kinds of Tb(Ⅲ) complexes emit intense green fluorescence under ultraviolet light. The intensity order of the strongest emission peak
5
D
4
7
F
5
(545 nm) for these Tb(Ⅲ) complexes is: Tb
2
(p-PA)(p-MBA)
4
(phen)
2
H
2
O>Tb
2
(p-PA)(o-MBA)
4
(phen)
2
2H
2
O>Tb
2
(p-PA)(BA)
4
(phen)
2
2H
2
O>Tb
2
(p-PA)(m-MBA)
4
(phen)
2
2H
2
O.
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).[2] Yang X P, Hahn B P, Jones R A, et al. Synthesis of an octanuclear Eu(Ⅲ) cage from Eu2+4:Chloride anion encapsulation, luminescence, and reversible MeOH adsorption via a porous supramolecular architecture [J]. Inorg. Chem., 2007, 46 (17):7050-7054.[3] Yang X P, Jones R A, Rivers J H, et al. Syntheses, structures and luminescent properties of new lanthanide-based coordination polymers based on 1,4-benzenedicarboxylate (bdc) [J]. Dalton Trans., 2007, (35):3936-3942.[4] Zhang Zhenghua, Wan Shuangyi, Okamurab Taka-aki, et al. Synthesis and crystal structure of two lanthanide complexes with benzenecarboxylic derivatives [J]. Z. Anorg. Allg. Chem., 2006, 632 (4):679-683.[5] Tan Hui, Wang Liying, Zhou Yue, et al. Synthesis and optical properties of complexes of terbium with aromatic compounds and succinic acid [J]. Chin. J. Lumin. (发光学报), 2009, 30 (1):101-107 (in Chinese).[6] Zhang Jianjun, Wang Ruifen, Bai Jihai, et al. Thermal decomposition mechanism and non isothermal kinetics of complex of La2(p-MBA)6(phen)22H2O [J]. J. Rare Earths, 2002, 20 (5):449-452.[7] Ren Xiaoming, Wei Changping, Wang Peng, et al. Preparation and fluorescence properties of ternary complexes of Eu(BA)3PIP and Eu(BA)3phen [J]. Chin. J. Lumin. (发光学报), 2009, 30 (2):252-256 (in Chinese).[8] Wang Ruifen, Wang Shuping, Shi Shikao, et al. Crystal structure and properties of a terbium benzoate complex with 1,10-phenanthroline [J]. Chin. J. Struct. Chem. (结构化学), 2004, 23 (11):1300-1304 (in Chinese).[9] Xu Lijuan. Synthesis, structure and properties of rare earth halogen-benzoic acid complexes . Shijiazhuang: Hebei Normal University, 2007.[10] Gao Zhihua. Synthesis, structure and luminescence properties of rare earth aromatic carboxylic acids complexes . Shijiazhuang: Hebei Normal University, 2005.[11] Latva M, Takalo H, Mukkala V M. Correlation between the lowest triplet state energy level of the ligand and lanthanide(Ⅲ) luminescence quantum yield [J]. J. Lumin., 1997, 75 (2):149-169.[12] Ma Ruixia. Synthesis, structure and luminescence properties of europium aromatic carboxylic acids complexes . Shijiazhuang: Hebei Normal University, 2006.[13] Tsaryuk V, Zolin V, Legendziewicz J. The structure of ligand and effects of the europium luminescence excitation [J]. J. Lumin., 2003, 102-103 :744-750.
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