Reduced Molybdenum Phosphates Research Articles

ChemInform Abstract: Reduced Molybdenum Phosphates: Octahedral-Tetrahedral Framework Solids with Tunnels, Cages, and Micropores

ChemInform Abstract: Reduced Molybdenum Phosphates: Octahedral-Tetrahedral Framework Solids with Tunnels, Cages, and Micropores

ChemInform Abstract: Structural Characterizations and Magnetic Properties of Three New Reduced Molybdenum Phosphates.

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Synthesis and characterization of two new inorganic–organic hybrid cobalt molybdenum(V) phosphates

Two new inorganic–organic hybrid cobalt phosphomolybdates (Hdien)2[Co(dien)]2[Co(dien)(H2O)]2[CoMo12O24(HPO4)2(H2PO4)2(PO4)4(OH)6] ··· 5H2O (1) and (H2dien)2[Co(dien)]2[Co(H2O)2]2[CoMo12O24(HPO4)4(PO4)4(OH)6] ··· 7H2O (2) (dien = diethylenetriamine), involving molybdenum in the V oxidation state and covalently bonded transition metal complexes, have been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) chain framework, in which dien molecules adopt two kinds of coordination modes. Compound 2 shows a two-dimensional (2D) layer framework with three types of unusual tunnels. To the best of our knowledge, it is the first time [Co(dien)] units are directly incorporated into 1D and 2D skeletons of reduced molybdenum phosphates. The electrochemical properties of the two compounds were studied via the method of bulk-modified carbon paste electrodes. Furthermore, the magnetic properties of compound 2 are reported.

Structural characterizations and magnetic properties of three new reduced molybdenum phosphates

Three new molybdophosphates, [Co(dien) 2]·(H 3dien) 6·{[CoMo 12O 24(OH) 6(HPO 4) 2(PO 4) 6][Co(Hdien)] 2[CoMo 12O 24(OH) 6(PO 4) 8]}·(dien)·4H 3O·5H 2O ( 1), (H 3dien) 4[ MMo 12O 24(OH) 6(HPO 4) 4(PO 4) 4]·10H 2O [ M=Co for ( 2), Ni for ( 3); dien=diethylenetriamine], have been synthesized by employing hydrothermal method and characterized by single crystal X-ray diffraction. Compound 1 is built up of Co[P 4Mo 6] 2 units as the structural motif covalently linked by [Co(Hdien)] complex subunits to yield an unusual 1-D chain. Compounds 2 and 3 are isomorphic and both display covalent discrete M[P 4Mo 6] 2 cluster structures which are linked by the hydrogen bonds to form 3-D supramolecular networks. Both 1 and 2 display antiferromagnetic interaction and these three compounds all exhibit intensive photoluminescence.

Self-assembly of four three-dimensional reduced molybdenum(V) phosphates decorated with transitional metal complexes

Four new three-dimensional materials built from reduced molybdenum(V) phosphates as building blocks and transitional metal (Co, Zn and Cd) complexes as linkers, (Hbpy) 2[Co(bpy)(H 2O)] 2[Co(H 2PO 4) 2 (HPO 4) 6(MoO 2) 12(OH) 6] ( 1), [Co(H 2O) 4] 2[Co(Hbpy)(H 2O)] 2[Co(bpy)][Co(HPO 4) 4(PO 4) 4(MoO 2) 12(OH) 6] · 6H 2O ( 2), Na 2[Zn(Hbpy)(H 2O) 2] 2[Zn(Hbpy)] 2[Zn(HPO 4) 2(PO 4) 6(MoO 2) 12(OH) 6] · 4H 2O ( 3), (H 2bpy) 2[Cd(bpy)(H 2O)] 2[Cd(bpy)(H 2O) 2] 2[Cd(HPO 4) 4(PO 4) 4(MoO 2) 12(OH) 6] · 2H 2O ( 4) (bpy = 4,4′-bipyridine), have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. The 3-D framework of 1 is constructed from Co[P 4Mo 6] 2 dimers bonded together with [Co(bpy)] n coordination polymer chains. In compound 2, the Co[P 4Mo 6] 2 dimers are linked by both [Co(bpy)] complex chains and the cobalt dimers to form a 3-D framework. Compounds 1 and 2 represent the first examples of reduced molybdenum(V) phosphates decorated with transition metal complexes chains. The 3-D framework of 3 is constructed from Zn[P 4Mo 6] 2 dimers bonded together with [Zn(bpy)] coordination complexes and [Zn(bpy)(H 2O) 2] complexes. In compound 4, the Cd[P 4Mo 6] 2 dimers are coordinated with [Cd(bpy)(H 2O)] and [Cd(bpy)(H 2O) 2] complexes to construct a 3-D structure. To our best knowledge, it is the first time that linear ligand 4,4′-bpy molecules have been grafted into the backbone of reduced molybdenum phosphates. Furthermore, the magnetic properties of compounds 1 and 2 are reported.

Reduced molybdenum phosphates: synthesis, characterization and magnetic properties

A synthetic pathway to obtain pure phases of reduced molybdenum phosphates in air is described. Starting from mixtures of MoO 3 and (NH 4) 2HPO 4 with different molar ratios Mo/P, and controlling the time and temperature of heating, the compounds: MoOPO 4, (MoO) 2P 4O 13, MoP 2O and Mo(PO 3) 3 have been prepared. Their spectroscopic and magnetic properties are discussed on the basis of the structural features. Both a significant effect of the spin-orbit coupling and the existence of antiferromagnetic interactions, propagated via the ∥PO 4∥ groups, have been observed.

Reduced molybdenum phosphates: octahedral-tetrahedral framework solids with tunnels, cages, and micropores

Reduced molybdenum phosphates: octahedral-tetrahedral framework solids with tunnels, cages, and micropores