Journal
DALTON TRANSACTIONS
Volume 39, Issue 27, Pages 6276-6284Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt00031k
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Funding
- Natural Science Foundation of Heilongjiang Province [ZD200903]
- Scientific Fund for Remarkable Teachers of Heilongjiang Province [1054 G036]
- Program for New Century Excellent Talents in University [NCET-06-0349]
- University of Heilongjiang
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The first example of rare-earth organic frameworks with 3-aminopyrazine-2-carboxylic acid (Hapca) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PL, TG, powder and single-crystal X-ray diffraction. These ten complexes exhibit three different structure types with decreasing lanthanide radii: [La(apca)(3)](n) (1) for type I, {[Ln(apca)(ox)(H(2)O)(2)]center dot H(2)O} n (Ln = Pr (2), Nd (3), ox = oxalate) for type II, and [Ln(2)(apca)(4)(OH)(2)(H(2)O)(2)](n) (Ln = Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Y (10)) for type III. The structure of type I consists of 1D snowflake chains along a-axis, which are further interconnected by hydrogen bonds to produce a 3D sra net topology containing infinite (-C-O-La-)(n) rod-shaped SBU. Type II has 2D Ln-apca-ox 4(4)-net, in which a planar udud water tetramers (H(2)O)(4) are formed by coordinated and free water molecules. Type III also comprises of 2D 4(4)-layer network constructed from Ln-apca-OH. The structure diversity is mainly caused by the variation of coordinated ligand and lanthanide contraction effect. Remarkably, the oxalate in type II was in situ synthesized from 3-aminopyrazine-2-carboxylic acid through an oxidation-hydrolysis reaction. The luminescent investigations reveal that complex 1 exhibits strong blue emission and complex 5 exhibits characteristic luminescence of Eu(3+).
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