Design, Syntheses, Structures, And Properties Of Several Transational Metal-Organicphosphonate Compounds

Widely used industrial and agricultural product herbicide glyphosate, and corrosion inhibitors such as hydroxy ethylidene diphosphonic that acid (HEDP), amino trimethylene phosphonic acid (ATMP), hexamethylene diamine tetramethyl phosphonic acid (HDTMPA) are chosen as organic ligands to synthesize metal complexes in this paper. Hydrothermal, solvothermal, aqueous and non-aqueous synthetic methods are all used for the research. Some progresses achieved are listed below.1. A watersoluble "sandwich-type" polymolybdenumphosphate [(C2H5)4N]6{NaMo12O24(OH)6(PO4H)2(PO4H3/2)6]}·14.32H2O(1) was attained by hydrothermal synthetic method, in which, the materials were molybdenum, hydroxy ethylidene diphosphonic acid (HEDP), sodium molybdate and tetraethyl ammonium bromide. The sandwich-type molybdate contains a single set of M[Mo6P4]2 building blocks as the anion, and it is water soluble. These features make the compound expectful to become the first case of raw material to design and synthesize compounds containing the general building blocks of M[Mo6P4O31]2.2. By using the Strategy of Oxidizing Mo-Mo bands, three isomorphic tetramolybdenum compounds with general anionic formula of {M[MoⅥ2O6CH3C(O)(PO3)2]2}n- (M=FeⅢ(2); CrⅢ(3); Mn" (4)) containing two{MoⅥ2O6} units were achieved, in which, [Mo2O4(H2O)]2+and (NH4)8{MoⅤ2O4[(MoⅥ2O6)CH3C(O) (PO3)2]2}·6.65H2O (5) were used as the original reagents. The successful syntheses of the three isomorphic compounds 3-4 were proved a successful strategy of designing new POMs containing{MoⅥ2O6}.3. Two mononuclear pentacoordinated Cu (Ⅱ) complexes: Cu(H2O)(2,2'-bpy)CH3C(OH)(PO3H)2·2H2O (bpy=C12H8N2) (6), Cu(H2O)(1,10-phen)CH3C(OH)(PO3H)2·2H2O (1,10-phen=C12H8N2) (7), and three heteronuclear Cu(Ⅱ)-Mo(Ⅵ) complexes Cu2(H2O)2(2,2'-bpy)2MoO2[CH3C(OH)(PO3H1/2)2]2·10H2O (8), Cu2(H2O)2(2,2'-bpy)2MoO2[N(CH2PO3)3]·1.22H2O (bpy= C10H8N2) (9), and Cu2(H2O)2(1,10-phen)2MoO2[N(CH2PO3)3]·2.5H2O (1,10-phen=C12H8N2) (10) were achieved under traditional hydrothermal experiments at 120℃for 4 days. Compounds 6-10 were characterized by IR, UV-Vis, Elemental analysis, ICP, UV-Vis, Single X-ray diffraction analysis, and Electrochemistry.4. A compound [FeⅡ(bipy)3][Fe2Ⅱ(ox)3] (11) with 3D networks was achieved by hydrothermal synthetic mehod and characterized by IR and single X-ray crystal diffraction analysis at low temperature. Compared with the reported light catalytic synthesis method, hydrothermal mehod is more efficient and convenient. After many experiments, we found that the growth and shape of crystals depend on temperature and pH.