YIN Ming-cai, LI Ming, YUAN Liang-jie, SUN Ju-tang. Synthesis and Luminescence Properties of Tb-Zn One-dimension Coordination Polymers[J]. Chinese Journal of Luminescence, 2005,26(4): 448-454
YIN Ming-cai, LI Ming, YUAN Liang-jie, SUN Ju-tang. Synthesis and Luminescence Properties of Tb-Zn One-dimension Coordination Polymers[J]. Chinese Journal of Luminescence, 2005,26(4): 448-454DOI:
Many aromatic carboxylate coordination compounds of rare earth have eximious photics
magnetics and catalysis properties in virtue of the structural multiformity. The 4f-3d hetero-metallic coordination polymers with particular structure mostly exist in dimer or multimer
and have latent application foreground at magnetism and luminescence materials. This paper aims to select α-furancarboxylic acid (HFur) and α-thiophenecar-(boxylic) acid (Htpca) with biggish conjugation system as ligands
1
10-phenanthroline (phen) as cooperative (ligand
) Zn
2+
ion as sensibilizer of Tb
3+
ion luminescence
to synthesize 4f-3d hetero-metallic coordination (polymers) in the nature of excellent luminescent performance and good dissolubility
to investigate the influence of crystal structure and coordination field on the spectrum character. The 1-dimension coordination polymers Tb(Fur)
3
(H
2
O)
2
·DMF and Tb
2
Zn(Fur)
8
(H
2
O)
2
and tetranuclear heterometallic complex Tb
2
Zn
2
-((tpca)
10
)(phen)
2
were prepared by the rheological phase reaction method. These complexes have good dissolubi(lity in water) and/or organic solvents
and emit very strong green luminescence under ultraviolet excitation. The crystal structures were characterized with single crystal and powder X-ray diffraction. The ultraviolet(visible) absorption and fluorescence spectra were measured. In these polymers the metallic atoms are linked by means of carboxylate groups (-CO
2
-
) with bidentate bridging and tridentate chelating-bridging
and the chain structures …Tb…Tb…
…Zn…Tb…Tb…Zn…Tb…Tb… and Zn…Tb…Tb…Zn were formed
respectively. The Tb
3+
ions are in 8-coordination
9-coordination and 7-coordination configuration
respectively. The average bond length of Tb-O are 0.239 5(4)
0.247 4(5) and 0.231 8(4) nm. It was revealed that Tb
3+
ion in the coordination polymers with 1-dimension chain structure could generate very strong direct (excited) emission; when Zn
2+
ion was inserted in …Tb…Tb… chain
the energy transfer between Tb
3+
ions was weakened but the energy transfer from ligand to rare earth ion was enhanced. In the coordination compound without bridging (or bridge-chain) structure between Tb
3+
ions
the direct excited emission of Tb
3+
ion can not occur. In addition
in the low symmetric and strong coordination field of 7-coordinate geometry
7
F
J
energy level of Tb
3+
arose greater split
but in the case of 8-and 9-coordination it not split or small split.