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
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): 908-913DOI:
Synthesis and Fluorscence of Quaternary Europium and Terbium Complexes with Aromatic Carboxylic Acid and 1,10-phenanthroline
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.
关键词
Keywords
references
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.