Ionothermal Synthesis And Properties Of Polyoxometalate Based Three-dimensional Entangled Compounds

Polyoxometalates(POM) is a kind of unique cluster compounds constructed by former transition metal ions which connect directly to the oxygen atom on the octahedral.They have wide application and broad development prospects in catalytic chemistry,medicine chemistry, optical, magnetic electrochemical and any other fields, owing to its rich structure and kinds of chemical and physical properties. In addition, it has attracted people to construct the hybrid materials with novel structure and excellent properties as a basic building unit.In this paper, we have successfully obtained five Polyoxometalates based compounds with different structure under ionthermal conditions choosing different type POM as the basic building unit, different kinds of orgniac ligands and Cu?Zn?Ag cations.Therefore, the photocatalytic, nitrogen adsorption and luminescent properties of these compounds have been also studied. We expound the pH of these reactions, the temperature of these reactions and the ratio of the reactant influence to the structure and nature of these compounds in detail.1. Four novel POMs-based metal-organic frameworks have been synthesized under ionothermal conditions using Keggin-type units as second building block, BBTZ and BTMB as organic ligands with Cu and Zn cation.[CH2BTMB]2[CuBTMB][PMo?9Mo?3O40](1)BTMB = 4,4?-bis((1H-1,2,4-triazol-1-yl)methyl)biphenyl[Zn(H2O)(BTMB)2][Zn(BTMB)2Cl]BTMB[PMo12O40]·2H2O(2)BTMB = 4,4?-bis((1H-1,2,4-triazol-1-yl)methyl)biphenyl[Zn2(H2O)2(BTMB)3][PMo?11Mo?O40](3)BTMB = 4,4?-bis((1H-1,2,4-triazol-1-yl)methyl)biphenyl BBTZ[(Cu?BBTZ)2(PMo12O40)]·H2O(4)BBTZ = 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzeneCompounds 1, 2, 3 and 4 were prepared by the same Keggin Polyoxometalates,different organic ligands and metal cations under ionothermal conditions through adjusting the pH and temperature of these reactions and the ratio of these reactants.Compound 1 and 2 both emerge novel entangled polyrotaxane structure. Compound 3-4both emerge 3D supramolecular porous structures. Whereby, the 3D supramolecular porous structure of 3 and 4 was constructed by 4,4 topological monolayers and by 6,6honeycomb monolayers, respectively.2. An unusual 3D self-interpenetration organopolymolybdate polymer throughMo-N bond has been obtained by ionothermal method using octamolybdate-type POM as a second building unit, BBTZ as the organic ligand and Ag cation as the metal center.[AgBBTZ][MoVMo3VIO12](5)BBTZ = 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)benzeneCompound 5, which is an organopolymolybdate polymer using octamolybdateas the basic building unit based on ?-[Mo8O24]2- has been obtained under ionoth ermal condition for the first time. In this compound, the organic ligand BBTZ c oordinated directly to the Polyoxometalates. In addition, we have studied the N2 adsorption, luminescent properties of this compound.