| Heteropoly phosphor-molybdic polyanions are regard as one of the attractive building blocks with a virtually unmatched range of physical and chemical properties appliance to diverse areas such as catalysis,optics,electronic and magnetism.One of the remarkable approaches to designing and constructing POM-base hybrid compounds with unique structure is to combine POMs with transition-metal ions.In this paper,11 new {P4Mo6}-based POM structures 1-11 have been synthesized by hydrothermal method.Among them,ten novel compounds have been synthesized by using in-situ generated viologen as the organic templates.Compounds 1-11 have been structurally characterized by IR,UV-vis,elemental analysis,XRPD and single-crystal X-ray diffraction.Moreover,the thermal properties,magnetic properties and electrochemical behavior have also been investigated in detail.The main texts are as follows:1.Four novel 3D inorganic-organic hybric compounds 1-4 based on tetrameric {P4Mo6} clusters Co-{P4Mo6}-MV-1,Mn-{P4Mo6}-MV-2,Co-{P4Mo6}-EV-3,Mn-{P4Mo6}-EV-4 have been prepared by using in-situ generated methyl viologen(compounds 1-2)and ethyl viologen(compounds 3-4)cations as templates,in which the templates induce the generation of the three-dimensional structure:H5[C12H116N2]4[Co4(PO4)(H2O)4Na2][Co2(Mo6O12(HPO4)3(PO4)(OH)3)4]·12H2O(1)H5[C12H16N2]4[Mn4(PO4)(H2O)4Na2][Mn2(Mo6O12(HPO4)3(PO4)(OH)3)4]·12H2O(2)H5[C14H20N2]4[CO4(PO4)(H20)4Na2][CO2(Mo6O12(HPO4)3(PO4)(OH)3)4]·12H2O(3)H5[C14H20N2]4[Mn4(PO4)(H2O)4Na2][Mn2(Mo6O12(HPO4)3(PO4)(OH)3)4·12H20(4)Compounds 1-4 possess 3D porous structures baseed on tetrametric{[M4(PO4)(H2O)4Na2](?)[P4Mo6O31]4} cluster.in witch each anion cluster is considered as an four-connected node with metal ions as linkers.The voids left by packing the anions together form an unusual array of three-dimensional tunnels,which are filled with viologens MV2+/MV2+ ions.The large voids formed by a single 3D network alow incorporation of another identical network.The essence of the interpenetration is that the second net is located,equally spaced,along the c-axis of the first net.Compounds 1-4 are insoluble in most conventional solvents and the thermal decomposition temperature of the inorganic framework is above 800℃.They exhibit good electrocatalytic activity toward the reduction of hydrogen peroxide and sodium nitrite.2.Two different novel frameworks 5-6 have been hydrothermally synthesized in the mixed solvent of H20 and alcohol at 170～180 ℃ by the reaction of the {P4Mo6} clusters and transition-metal ions Zn2+ by using in-situ generated viologen as the organic templates.H21[C14H20N2]3[Zn4(H20)2][Na12(PO4)(H2O)12][Zn0.5(P4Mo6O31)]4(5)H40[C12H16N2]2[ZnNa2(H2O)2][Zn(P4Mo6O31)]2·H2O(6)Compound 5 is a 3D porous structure based on tetrametric {P4Mo6} cluster and[Na12PO4(H2O)12]core in which ethyl viologen fill in the channels.Methyl viologen of compound 6 locate in the interlayer as templates and counterions.Thermogravimetric analyses(TGA)of 5 and 6 exhibit a continuous weight loss corresponding to the calculated value and structural characteristics.Compounds 5 and 6 exhibit good electrocatalytic activities for the reduction of nitrite.3.The {Mo2O42+} has been selected as precursor,five novel inorganic-organic hybric compounds 7-11(Fe-{P4Mo6}-MV-7,Cd-{P4Mo6}-MV-8,Na3-{P4Mo6}-MV-9,Na-{P4Mo6}-MV-10,Ni-{P4Mo6}-bpp-11)containing {M[P4Mo6031]12-} units have been prepared under solvothermal method.Compounds 7-10 are synthesizd by using in situ generated methyl viologen ion as the templates and counterions.Compound 7 displays two dimensional network;compounds 8 and 9 exhibit 1D chain structures;compound 10 displays sandwich-type dimer structure.Compound 11 forms a three-dimensional inorganic framework,in which the protonated bpp(bpp=l,3-bis(4-pyridyl)propane)fill in the cavity.The electrochemical behaviors and the electrocatalytic reduction of hydrogen peroxide and sodium nitrite of 7-11(7-CPE,8-CPE,9-CPE,10-CPE,11-CPE)have also been investigated. |
PDF Full Text Request