Synthesis And Characterization Of Metal Phosphite And Phosphonates Microporous Compounds

Inorganic-organic hybrid materials has been a research field of rapid expansion in recent years, which is mainly due to the potential application in the area of catalysis, adsorption and separation. Design and synthesis of new inorganic-organic hybrid materials, to explore the relationship between structures and properties, screening of new materials with practical significance is important.As metal phosphite and phosphonate with the structure of the richness and diversity of composition have been widely applied in many areas, so we have focused our study on the syntheses of two classes of inorganic-organic hybrid materials: metal phosphite incorporating organic ligands and metal phosphonate. By hydrothermal method and solvent evaporation method we have prepared the nine microporous compounds. The structures of these compounds have been determined by single-crystal X-ray diffraction, and further characterized by IR, elemental analysis, and thermogravimetric analysis. The results will be introduced in the following issue.1.Two zinc phosphite hybrid materials, namely, (C3H10N)2·[Zn3(HPO3)4](1) and (C13H16N2)·[Zn3(HPO3)4](2) have been synthesized using propylamine and 4,4'- (1,3 - propanediyl)bis-pyridine as template agents. Complex(1) crystallizes in Orthorhombic system with space group Pccn. The connectivity of the ZnO4and HPO3 tetrahedra results in a two-dimensional layed structure,which are further linked by inifinite corner-sharing 4-membered ring chains to form a 3-D structure that with 16-membered ring channels. The protonated amine molecules sit in the middle of the channels and interact with the framework via hydrogen bonds. Complex(2) crystallizes in Monoclinic system with space group P2(1)/c. The connectivity of the ZnO4 and HPO3 tetrahedra results in a two-dimensional layed structure. The protonated amine molecules sit in the interlayer, and connect with the inorganic layers through hydrogen bonds.2.A new three-dimensional calcium diphosphonate, Ca(H2O)3[C6H4(CH2PO3H)2](3), have been synthesized from p-xylenediphosphonic acid. Complex(3) crystallizes in Monoclinic system with space group C2/c. The three metal diphosphonates were hydrothermally synthesized based on p-xylenediphosphonic acid, 1,10-phen and 2,2′-bipy. Namely,Zn[C6H4(CH2PO3H)2](1,10-phen)2·C6H4(CH2PO3H2)2(4),Co[C6H4(CH2PO3H)2](1,10-phen)2·C6H4(CH2PO3H2)2(5)andCo[C6H4(CH2PO3H)2](2,2′-bipy)2·C6H4(CH2PO3H2)2(6). Complex(4-6) crystallizes in Monoclinic system with space group C2/c. The novel one-dimensional construction is simply built up from octahedral [ZnN4O2] which connected by the organophosphorus ligand. The framework has a channel system filled by guest p-xylenediphosphonic acid molecules that are bound to the framework through hydrogen bonds.3.The three transition metal diphosphonates were synthesized by using 1-hydroxyethylidenediphosphonic acid as the phosphonate ligands and by using triethylenediamine as template agents. Namely, {[Co(HO3P-C(OH)(CH3)-PO3H)2]·2H2O}·C6H14N2·8H2O(7),{[Zn(HO3P-C(OH)(CH3)-PO3H)2]·2H2O}·C6H14N2·8H2O(8)and{2[Ni(HO3P-C(OH)(CH3)-PO3H)2]·4H2O}·2C6H14N2·9H2O(9). Complex (7-9) crystallizes in Triclinic system with space group P-1. The compound(7-9) exhibits a mononuclear structure. The center metal, sitting in a special position, is coordinated by four O atoms from two equivalent diphosphonate ligands and two O atoms from two equivalent water molecules. In the lattice, the mononuclear species are hydrogen-bonded to each other, leading to a supramolecular anionic network which is stabilized by (C6H14N2)2+ cations and water molecule through hydrogen bondings.