Synthesis, Crystal Structures And Properties Of New Metal Phosphonate Coordination Polymers

The design and construction of novel functional hybrid materials based on metal phosphonates has attracted considerable attention in recent years due to the possibility to form interesting structures with potential applications in the areas of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry and materials chemistry.In this work, thirteen new phosphonate coordination polymers with 1-hydroxyethylidenediphosphonic acid (hedpH4),2-hydroxyphosphonoacetic acid (HPAA) and H2O3PCH2-NC5H9-COOH have been synthesized under mixed-solvothermal and hydrothermal conditions, respectively. Then they were structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy and elemental analysis. Luminescence properties of compounds 4,7,8,9 and 10 have also been studied. The chemical constitution formulas are listed as follow: (1)Mn(hedpH2)3·3NH2(CH3)2·NH(CH3)3·3H20 (2)Co(hedpH2)3·3NH2(CH3)2·NH(CH3)3·3H20 (3)Ni(hedpH2)3·3NH2(CH3)2·NH(CH3)3·3H2O (4)Zn(hedpH2)3·3NH2(CH3)2·NH(CH3)3·3H2O (5)[Mg(hedpH2)2(H2O)]·2NH2(CH3)2 (6)[Cu(hedpH2)2(H2O)]·2NH2(CH3)2 (7) Zn3(hedp)2·2NH2(CH3)2·H2O (8) [Zn2(HO3PCH(OH)CO2)3]·2NH2(CH3)·3H2O (9)Cd1.5[(03PCH2NHC5H9COO)(OOCC6H4COO)0.5] (10)Pb4[(HL)(L)(OOCC6H4COO)1.5]·2H2O (11)La3[(HL)2(H2L)(OOCC6H4COO)2(H2O)]·7H2O (12)Ce3[(HL)2(H2L)(OOCC6H4COO)2(H2O)]·7H2O (13)Nd3[(HL)2(H2L)(OOCC6H4COO)2(H2O)]·7H2OCompounds 1-7 with 1-hydroxyethylidenediphosphonic acid (hedpH4) have been synthesized under mixed-solvothermal conditions. X-ray single crystal diffraction reveals that compounds 1-4 are isomorphic compounds, and they are zero-dimensional structure through hydrogen bonds forming a three-dimensional supramolecular structure. Compounds 5 and 6 are also zero-dimensional structure through hydrogen bonds forming a three-dimensional supramolecular structure. Compound 7 is a three-dimensional framework structure. Compound 8 with 2-hydroxyphosphonoacetic acid (HPAA) has also been synthesized under mixed-solvothermal conditions. X-ray single crystal diffraction reveals that compound 8 is a two-dimensional layered structure. By introduction of 1,4-benzenedicarboxylic acid as a second organic ligand, compounds 9-13 with H2O3PCH2-NC5H9-COOH have been synthesized under hydrothermal conditions. X-ray single crystal diffraction reveals that compounds 9 and 10 are a three-dimensional framework structure. Compounds 11-13 are isomorphic compounds; they are also a three-dimensional framework structure. Compound 13 was not obtained single crystals suitable for X-ray structural analysis, however, X-ray powder diffraction analysis indicates compound 13 is isomorphous and exhibit a three-dimensional framework structure, which is same to the structure of compounds 11 and 12. The luminescence analyses indicate that compounds 4,7, 8,9 and 10 are good candidate for luminescent material.