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Zhang Z.,Key Laboratory of Polyoxometalate Science | Liu J.,Key Laboratory of Polyoxometalate Science | Li Y.,Key Laboratory of Polyoxometalate Science | Yao S.,Key Laboratory of Polyoxometalate Science | And 2 more authors.
Journal of Solid State Chemistry | Year: 2010

Two entangled compounds [(bpy)6CuI 6Cl3(MoVW5O19)] (1) and [(bpy)7CuI 7Cl2(BW12O40)]·H2O (2) (bpy=4,4′-bipyridine), have been successfully synthesized under hydrothermal conditions and characterized by element analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction analyses. Compound 1 represents the first eight-connected self-penetrating network constructed from cuprous chloride clusters [Cu6Cl3] and Lindquist-type polyoxoanions. Compound 2 exhibits an interesting fivefold interpenetrating network consisting of Keggin polyoxoanions and Cu+-metal-organic framework. Crystal data of the two compounds are following: 1, triclinic, P over(1, -), a=11.502(2) Å, b=13.069(3) Å, c=13.296(3) Å, α=90.55(3)°, β=113.74(3)°, γ=110.48(3)°, Z=1; 2, triclinic, P over(1, -), a=12.341(3) Å, b=13.119(3) Å, c=15.367(3) Å, α=99.12(3)°, β=90.53(3)°, γ=104.49(3)°, Z=1. Crown Copyright © 2009.


Liu L.,Key Laboratory of Polyoxometalate Science | Li F.,Key Laboratory of Polyoxometalate Science | Xu L.,Key Laboratory of Polyoxometalate Science | Liu X.,Key Laboratory of Polyoxometalate Science | Gao G.,Key Laboratory of Polyoxometalate Science
Journal of Solid State Chemistry | Year: 2010

Two new polyoxometalate compounds [(CH3)4N]8[Ln(H2O)8]2[(α2-As2W17O61)Ln(H2O)2]2·nH2O (Ln=Er (1), Dy (2)) have been prepared by the trivacant Dawson-type anion [α-As2W15O56]12- and trivalent rare earth ion and characterized by single-crystal X-ray diffraction, IR spectra, thermogravimetric and electrochemical analyses. The centrosymmetric polyoxoanion, {[(α2-As2W17O61)Ln(H2O)2]2}14-, bounded to each other via Ln3+ connecting to terminal W-O oxygen atoms. Furthermore, the polyoxoanions are linked by [Ln(H2O)8]3+ to form an extensive 3D supramolecular network structure depending on hydrogen bond. The magnetic properties of the two compounds have been studied by measuring their magnetic susceptibilities in the temperature range 2.0-300.0 K, indicating the depopulation of the stark components at low temperature and/or very weak antiferromagnetic interactions between magnetic centers. Low-temperature ac magnetic susceptibility measurements reveal a slow magnetic relaxation behavior for 2. © 2009 Elsevier Inc. All rights reserved.


Zhao S.,Key Laboratory of Polyoxometalate Science | Wang X.,Key Laboratory of Polyoxometalate Science | Huo M.,Northeast Normal University
Applied Catalysis B: Environmental | Year: 2010

Micellar molybdovanadophosphoric polyoxometalate (POM) catalysts [(CnH2n+1)N(CH3)3]3+xPVxMo12-xO40 (x = 1, 2, 3; n = 8, 12, 14, 16, 18) were prepared and used for catalytic wet air oxidation (CWAO) of phenol. X-ray photoelectron spectrum (XPS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) were used to characterize the resulting samples. The best catalytic activity was obtained over (C16TA)6PV3Mo9O40, which showed 95.3% degradation efficiency, 98.5% COD removal and 93.0% TOC reduction with air under room condition toward complete degradation product CO2 within 90 min. The leaching test showed that the POM micellar catalysts have an excellent stability and can be used as heterogeneous catalysts for about six times. © 2010 Elsevier B.V. All rights reserved.


Zhang P.-P.,Key Laboratory of Polyoxometalate Science | Peng J.,Key Laboratory of Polyoxometalate Science | Tian A.-X.,Key Laboratory of Polyoxometalate Science | Pang H.-J.,Key Laboratory of Polyoxometalate Science | And 4 more authors.
Journal of Molecular Structure | Year: 2010

Two new supramolecular compounds based on the Wells-Dawson polyoxometalate, [Cu(Hpbi)2]4[P2W18O62]2 (1) and (H2bbi)4[Cu2(bbi)(Hbbi)2][P2W18O62]2 (2) (pbi = 1,1′-(1,3-propanediyl)bis(imidazole), bbi = 1,1′-(1,4-butanediyl)bis(imidazole)), were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, and single X-ray diffraction. The [P2W18O62]6- polyanions in both compounds play the template role inducing the metal-organic coordination polymers to array around them. The polymers form 3D supramolecular frameworks with different voids in which the polyanions reside. The difference should be attributed to the different lengths of the two organic ligands. In addition, the electrochemistry properties of the two compounds were studied, which indicates that the supramolecular compounds keep the redox properties of their parent polyanions and exhibit the electrocatalytic activities toward the reduction of bromate and nitrite. © 2010 Elsevier B.V. All rights reserved.


Wang S.-M.,Key Laboratory of Polyoxometalate Science | Li Y.-W.,Key Laboratory of Polyoxometalate Science | Feng X.-J.,Key Laboratory of Polyoxometalate Science | Li Y.-G.,Key Laboratory of Polyoxometalate Science | Wang E.-B.,Key Laboratory of Polyoxometalate Science
Inorganica Chimica Acta | Year: 2010

The deep eutectic solvents synthetic method was initially explored as a facile synthesis route to prepare new polyoxometalate (POM)-based hybrids. Such a method can not only avoid poor solubility, lower yields and the potential explosion, but also act as a new type of noxious, convenient and environmental friendly organic reagents. Using the choline chloride/urea eutectic mixture as the deep eutectic solvents, two new compounds, [(CH3)3N(CH2)2OH]4[β-Mo8O26] (1) and {(N2H5CO)[(CH3)3N(CH2)2OH]2}[CrMo6O24H6]·4H2O (2), were successfully obtained at room temperature. Both compounds were fully characterized by elemental analyses, IR, UV-Vis, TG analyses, cyclic voltammetry and single-crystal X-ray diffraction. The crystal structures of both compounds exhibit 3-D supramolecular assembly based on the extensive hydrogen bonding interactions between organic cations and polyoxoanions. Compounds 1 and 2 represent the first POM-based hybrids prepared by the deep eutectic solvents synthetic method. © 2009 Elsevier B.V. All rights reserved.


Zhang L.-C.,Key Laboratory of Polyoxometalate Science | Zhang L.-C.,Liaoning Normal University | Xue H.,Liaoning Normal University | Zhu Z.-M.,Liaoning Normal University | And 4 more authors.
Inorganic Chemistry Communications | Year: 2010

Two new polyoxometalate-based estertin derivatives, Na6K4[{Sn(C3H4O2)}2{Sn(C3H4O2)(H2O)}2·(B-β-SbW9O33)2]·14H2O (1) and Na4K6[{Sn(C4H6O2)(H2O)}2(WO2)2(B-β-SbW9O33)2]·19H2O (2), have been synthesized by the reaction of Na9[B-α-SbW9O33]{bullet operator}19.5H2O with Cl3Sn(CH2)2COOCH3 or Cl3SnCH2CH(CH3)COOCH3 in an aqueous KCl solution. Both compounds exhibit the sandwich-type structural feature, in which the carboxyethyltin fragments are sandwiched by two B-β-[SbW9O33]9- units. Structural analyses reveal that the reaction process involves α → β isomerization of [SbW9O33]9- unit and the hydrolysis of estertin into carboxyethyltin group. Both compounds display good electrocatalytic activities toward the reduction of hydrogen peroxide, and compound 1 also shows good anti-tumoral activities in vitro. © 2010 Elsevier B.V. All rights reserved.


Wang S.-M.,Key Laboratory of Polyoxometalate Science | Chen W.-L.,Key Laboratory of Polyoxometalate Science | Wang E.-B.,Key Laboratory of Polyoxometalate Science | Li Y.-G.,Key Laboratory of Polyoxometalate Science | And 2 more authors.
Inorganic Chemistry Communications | Year: 2010

Three new polyoxometalate-based hybrids {[(CH3)3N(CH2)2OH]2(H3O)}[Na2(H2O)6][IMo6O24]·H2O 1, {Na2[(CH3)3N(CH2)2OH]4}[Al(OH)6Mo6O18]2·8NH2CONH2·4H2O 2 and {Na6(H2O)18[(CH3)3N(CH2)2OH]2(CON2H5)2}[NaMo7O24]2·4NH2CONH2·H2O 3 were successfully synthesized in the choline chloride/urea deep eutectic mixture at room temperature. Reactant quantities of water presents in the nonaqueous eutectic mixture solvent may influence the structure of the products. The three compounds are fully characterized by elemental analyses, IR, UV-vis, TG analyses, power X-ray diffraction and single-crystal X-ray diffraction. The photocatalytic properties of 1 and 2 are investigated. © 2010 Elsevier B.V. All rights reserved.


Wu Q.,Key Laboratory of Polyoxometalate Science | Li Y.-G.,Key Laboratory of Polyoxometalate Science | Wang Y.-H.,Key Laboratory of Polyoxometalate Science | Zhang Z.-M.,Key Laboratory of Polyoxometalate Science | Wang E.-B.,Key Laboratory of Polyoxometalate Science
Inorganic Chemistry Communications | Year: 2010

A new sandwich-type polyoxometalate (POM) K12Na1[(HPW7O28)2Mn]·17.5H2O (1) has been synthesized and characterized by elemental analysis, IR, TG, UV as well as single-crystal X-ray diffraction analysis. Compound 1 represents the first sandwich-type POM constructed by the penta-lacunary heptatungstophosphate [HPW7O28]8- moieties. Moreover, compound 1 exhibits good electrocatalytic properties to reduce the nitrite. © 2009 Elsevier B.V. All rights reserved.


Zang X.-S.,Key Laboratory of Polyoxometalate Science | Tan H.-Q.,Key Laboratory of Polyoxometalate Science | Wu Q.,Key Laboratory of Polyoxometalate Science | Li Y.,Key Laboratory of Polyoxometalate Science | And 2 more authors.
Inorganic Chemistry Communications | Year: 2010

A new butterfly-like compound K5Na2[Mo9V3O38]·9H2O 1 has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis, UV-vis spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammogram and single-crystal X-ray diffraction analysis. Compound 1 is a new butterfly-like molybdodivanadate composed by Mo (VI) and V (V) with the Mo/V ratio 3:1, the polyoxoanion [Mo9V3O38 ]7- can be described as two {MMo4O18} (M = Mo/V) units connected by one {V2O8} core. The photocatalyst property of compound 1 has been investigated, which shows a good photocatalyst for degradation of RhB. © 2010 Elsevier B.V.


Chen W.-L,Key Laboratory of Polyoxometalate Science | Chen B.-W.,Key Laboratory of Polyoxometalate Science | Tan H.-Q.,Key Laboratory of Polyoxometalate Science | Li Y.-G.,Key Laboratory of Polyoxometalate Science | And 2 more authors.
Journal of Solid State Chemistry | Year: 2010

Employing the ionothermal synthesis approach, three new transition-metal-containing polyoxotungstate hybrids: [Dmim]2Na3[SiW11O39Fe(H2O)]·H2O (Dmim=1,3-Dimethylimidazole) (1), [Emim]9Na8[(SiW9O34)3{Fe3(μ2-OH)2(μ3-O)}3(WO4)]·0.5H2O(Emim=1-Ethyl-3-meth-ylimidazole) (2) and [Dmim]2[HMim]Na6[(AsW9O33)2{MnIII(H2O)}3]·3H2O (Dmim=1,3-Dimethylimidazole; Mim=1-Methylimidazole) (3) have been synthesized in 1-ethyl-3-methyl imidazolium bromide ([Emim]Br) ionic liquids (ILs). Compound 1 possesses a 3-D open framework constructed from the mono-ironIII-substituted α-Keggin-type anion and the organic cations [Dmim]+ through the hydrogen bond interactions. Compound 2 contains a [{FeIII 3(μ2-OH)2(μ3-O)}3(μ4-WO4)] cluster surrounded by three [SiW9O34]10- ligands, eight sodium cations and nine dissociative [Emim]+ cations around the polyoxoanion. The polyoxoanion of 3 consists of a high-valent trinuclear-manganese (III)-substituted sandwiching polyoxoanion based on the [α-AsW9O33]9- units. All the compounds are characterized by elemental analyses, IR, UV-vis spectra, TG-DTA and XRD analyses. The XPS and EPR spectra of MnIII in 3 were studied. The photocatalytic and electrocatalytic properties, as well as the stabilities of 1-3 were also investigated. © 2009 Elsevier Inc. All rights reserved.

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