| Metal phosphonates are important organic-inorganic hybrid materials, which can exhibit a range of structures including molecular clusters, chains, layers, and three dimensional frameworks. This structural versatility is reflected in applications to areas as diverse as photochemistry, proton conductivity, ion exchange, intercalation chemistry, and catalysis. As an important subclass of metal phosphonates, oxometal organophosphonates not only have all good characteristics, but also have advantages of themself. So they have attracted a great deal of research interest.In this work, we not only have devoted effort toward hydrothermal synthesis, but also have attempted to use solvothermal synthesis. Two new functionalized oxometal phosphonate coordination polymers have been synthesized by solvothermal technique and direct reaction, using 1?hydroxyethylidenediphosphonic acid (hedpH4) and the carboxyphosphonic acid, HOOC–C5H9N–CH2PO3H2 (H3L) as ligand, while another ten new functionalized oxometal phosphonate coordination polymers have been synthesized by hydrothermal technique ,using 1?hydroxyethylidenediphosphonic acid (hedpH4) as ligand and 2,2′-bipyridine or1,10-phenanthroline as the second ligand. These coordination polymers are all structurally characterized by single?crystal X?ray diffraction as well as with X?ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Meanwhile, the luminescent properties of compounds (7), (8), (9) and (10) have also been studied. The chemical constitution formulas are listed as follow:(1) [(VO)(H2O){CH3C(OH)(PO3H)2}2]·2NH2(CH3)2(2) [Zn(2,2'–bipy)(VO2){CH3C(OH)(PO3)2}]·H2O(3) [Co0.5(1,10–Phen)1.5{CH3C(OH)(PO3H)(PO3)}3(VO)3(OH)]·4H2O(4) [(HOOCC5H9NCH2PO3)2Mo5O15]·4NH2(CH3)2(5) [Cu2(1,10–Phen)2{CH3C(OH)(PO3)(PO3H)}2MoO2(H2O)]·H2O(6) Cu(1,10–Phen){CH3C(OH)(PO3)(PO3H)}Mo0.5O(7) [Zn(2,2'–bipy){CH3C(OH)(PO3H)2}]·0.5H2O(8) [Zn(1,10–Phen){CH3C(OH)(PO3H)2}]·H2O(9) [Zn2(1,10–Phen){CH3C(OH)(PO3H)2}2]·H2O(10) [Zn(1,10–Phen){CH3C(OH)(PO3H)2}](11) [Cu(2,2'–bipy){CH3C(OH)(PO3H)2}(H2O)]·H2O(12) [Cu(1,10–Phen)CH3C(OH)(PO3H)2(H2O)]·H2O Compounds 1 and 4 are obtained by solvothermal technique, using 1-hydroxyethylidenediphosphonic acid (hedpH4) and the carboxyphosphonic acid, HOOC–C5H9N–CH2PO3H2 (H3L) as ligand, while compound 2,3,5,6,8,9,10,11 and 12 have been synthesized by hydrothermal technique using 1?hydroxyethylidenediphosphonic acid (hedpH4) as ligand and 2,2′-bipyridine or1,10-phenanthroline as the second ligand. X?ray diffraction analysis shows that compounds 3,6 and 12 are 1D chains, the other compounds are all 2D network. There are inter–molecular hydrogen bonds among compounds except the compound 2.The thermal analysis of these compounds indicates that they form the stabilized framework structure. Compounds (7), (8), (9) and (10) can all emit a blue fluorescent emission. |
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