A novel polyoxometalate-based composite compound [Ni(phen)2][Hphen](AsW12040) (phen = 1,10-phenanthroline) I has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, ESR spectroscopy...A novel polyoxometalate-based composite compound [Ni(phen)2][Hphen](AsW12040) (phen = 1,10-phenanthroline) I has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, ESR spectroscopy and single-crystal X-ray diffraction. Each structure unit of 1 consists of one polyoxoanion AsW12O40^3-, one free phenanthroline molecule and one coordination cation [Ni(phen)2]^2+. The title compound crystallizes in the orthorhombic system, space group F212121, with a = 12.2383(7), b = 21.0884(11), c = 22.3237(12) A, V= 5761.4(5) A^3, Mr = 3520.44, Z = 4, Dc = 4.059 g/cm^3, F(000) = 6204, g(MoKα) = 24.844 mm^-1, GOF = 1.022, the final R = 0.0376 and wR = 0.0742 (I 〉 2σ(I)) for 865 parameters and 9637 observed reflections with I 〉 2σ(I).展开更多
A new heteropolycomplex, K 6H 3[ZnW 11 O 40 Al]·9 5H 2O was prepared and characterized by means of elemental analysis, IR, UV spectroscopy, 27 Al NMR , electrochemistry and X ray crystall...A new heteropolycomplex, K 6H 3[ZnW 11 O 40 Al]·9 5H 2O was prepared and characterized by means of elemental analysis, IR, UV spectroscopy, 27 Al NMR , electrochemistry and X ray crystallography. The crystal of K 6H 3[ZnW 11 O 40 Al]·9 5H 2O is cubic, space group Fm 3m , with lattice constants a=b=c =2 144 8(2) nm, V =9 866(2) nm 3, Mo radiation, R =0 057 8 for 497 independent data with [ I>2δ(I) ]. The anion is of α type Keggin structure with C s symmetry.展开更多
For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated...For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated by means of polarograms,cyclic voltammetry,31P NMR and X-ray diffraction methods.The heteropolynier of PMo12 and AsMo12 converte to their β-isomers during isomerization reaction which were found to have antiacidolysis property.展开更多
Two charge-transfer complexes of 2a and 2b of Keggin type were synthesized and characterized by elemental analysis, IR spectra, UV spectra, XRD, TG-DSC; and were compared with Hquin-PW12. The primary structure of the...Two charge-transfer complexes of 2a and 2b of Keggin type were synthesized and characterized by elemental analysis, IR spectra, UV spectra, XRD, TG-DSC; and were compared with Hquin-PW12. The primary structure of the heteropolyanions had not been changed after the formation of the charge transfer complexes.展开更多
In this paper,One novel Keggin type polyoxomolybdate compounds have been hydrothermal synthesized:{[(CH3)2NH2]4(SiMo12O40)}[(CH3)2NH]·(DMF)0.5(1).The compound 1have been characterized by infrared spectrum,and the...In this paper,One novel Keggin type polyoxomolybdate compounds have been hydrothermal synthesized:{[(CH3)2NH2]4(SiMo12O40)}[(CH3)2NH]·(DMF)0.5(1).The compound 1have been characterized by infrared spectrum,and the two-dimensional infrared correlation spectroscopy.展开更多
The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic...The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic system with space group P , Mr=2117.73, a= 13.702(4), b=14.107(3), c=14.184(2) ; α=119.27(1), β=93.14(2), ;γ=110. 3(2)°, V=2154.29~3, Z=2, F(000)=1999, μ=36.39cm^(-1), Dc=3.26 g/cm^3. Final R factor is 0.0515. Mo(Ⅴ) is situated in two different edge-shared Mo_3O_(13) groups. The heteropoly blue was characterized by IR, UV, polarography, X-ray photoelectron spectra and ESR. All the results show that the structure of the heteropoly anion with Keggin structure remains unchanged basically in the process of reduction.展开更多
A cobalt paradodecatungstate [Co(H2O)5]2[Co(H2O)4]3[H2W12O42]·11H2O has been successfully synthesized and structurally characterized by X-ray crystallography. Structure analysis indicates that the title compo...A cobalt paradodecatungstate [Co(H2O)5]2[Co(H2O)4]3[H2W12O42]·11H2O has been successfully synthesized and structurally characterized by X-ray crystallography. Structure analysis indicates that the title compound is of monoclinic, space group P21/n, with a = 13.449(3), b = 19.585(4), c = 13.990(3) °A, = 113.79(3)°, V = 3371.8(12) °A^3, Z = 2, R = 0.0519 and wR = 0.1242. The title compound exhibits a novel 3D extended network structure constructed by interconnecting the paradodecatungstate polyanion [H2W12O42]^10- clusters and cobalt^11 coordination ions.展开更多
Three new inorganic-organic composite polyoxotungstates [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]-4H2O 3...Three new inorganic-organic composite polyoxotungstates [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]-4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847(3), b = 21.597(2), c = 20.1179(19)A, V= 12099(2)A^3, Z= 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1^- with a = 12.31150(10), b = 16.1954(4), c = 19.36290(10)A, α = 99.366(11), β =105.168(8), γ = 111.836(8)°, V = 3309.98(9)A3, Z = l, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5)A, β = 102.338(5)°, V= 4103(2)A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1-3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.展开更多
Two new hybrid polyoxotungstates, [Co(2,2'-bipy)3][a-H5PW11CoO40]-3H2O 1 and [Fe(2,2'-bipy)3]2[a-HBW12O40]-2.5H2O 2 (2,2'-bipy = 2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR,...Two new hybrid polyoxotungstates, [Co(2,2'-bipy)3][a-H5PW11CoO40]-3H2O 1 and [Fe(2,2'-bipy)3]2[a-HBW12O40]-2.5H2O 2 (2,2'-bipy = 2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co(2,2'-bipy)3]2+ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe(2,2'-bipy)3]2+ cations. The data for 1: orthorhombic system, space group Pbcn, a = 16.062(6), b = 27.278(10), c = 16.951(6)A, V = 7427(5)A3 and Z = 4; and those for 2: triclinic system, space group P1, a = 13.787(3), b = 17.857(5), c = 18.918(5)A, a = 88.009(12), β = 72.768(10), γ = 74.935(10)°, V = 4291(2)A3 and Z = 2.展开更多
The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using...The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper(I/) centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.展开更多
A new coordination compound, [{Nd(NMP)_2(H_2O)_6Cl}{Nd(NMP)_2(H_2O)_7}H (P_2Mo_(18)O_(62)) (NMP=N-methyl-2-pyrrolidone) was synthesized and characterized by elemental analyses, IR spectrum, and X-ray single crystal st...A new coordination compound, [{Nd(NMP)_2(H_2O)_6Cl}{Nd(NMP)_2(H_2O)_7}H (P_2Mo_(18)O_(62)) (NMP=N-methyl-2-pyrrolidone) was synthesized and characterized by elemental analyses, IR spectrum, and X-ray single crystal structural analysis. The crystal structure indicates that the title compound belongs to monoclinic space group C _c, with unit cell dimensions a =2.4528(5) nm, b =1.9495(4) nm, c =2.4405(5) nm, β =109.94(3)°, Z =4, V =10.970 (4) nm^3, D _c=2.262 g·cm^(-3), R 1=0.0676, wR 2=0.1441. The ESR spectrum of powder of the title compound at 110 K after being exposed to sunlight shows the signal of Mo^(5+), g =1.95. Cyclic voltammetry was measured in aqueous solution containing 0.1 mol·L^(-1) KCl as the supporting electrolyte and shows that the title compound undergoes two one-electron reversible reductions.展开更多
A 1D chain-like organic-inorganic hybrid rare earth derivative of polyoxometalate H0.5[Sm(H2O)6]0.25[Sm(H2O)5]0.25{[Sm(H2O)7][Sm(H2O)2(DMSO)][SiW11O39]}·4.5H2O has been firstly synthesized by reaction ...A 1D chain-like organic-inorganic hybrid rare earth derivative of polyoxometalate H0.5[Sm(H2O)6]0.25[Sm(H2O)5]0.25{[Sm(H2O)7][Sm(H2O)2(DMSO)][SiW11O39]}·4.5H2O has been firstly synthesized by reaction of α-K8SiW11O39.13H2O, HClO4, Sm2O3 with dimethyl sulfoxide (DMSO) and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. The neighboring polyanionic units {[Sm(H2O)7][Sm(H2O)2(DMSO)][SiWHO39]}^2- are bridged together to a 1D chain structure by means of [Sm(H2O)2(DMSO)]^3+ ion.展开更多
A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(...A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(3), V = 1865.6(6) 3, Dc = 2.445 g/cm3, Z = 1, ?= 2.660 mm-1, Mr = 2746.56, F(000) = 1328, R = 0.0569, wR = 0.1190 and GOF = 1.125. The results of X-ray crystal analysis and IR spectrum show that there exists strong interaction between the heteropolyanions [SiMo12O40]4- and coordination cations [Mn(DMSO)5H2O]2+ in solid state.展开更多
A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6(μ3- OH)3(en)3(H2O)6}(B-α-PW9O34)]-6H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and characterized by IR spectra, e...A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6(μ3- OH)3(en)3(H2O)6}(B-α-PW9O34)]-6H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis (TGA), single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124(5), c = 21.4427(4)A, γ = 120.000°, V = 7737.5(3)A3, Z = 6, GOF = 1.083, R (wR) = 0.0317 (0.0610). Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6(μ3-OH)3(en)3(H2O)6}(B-α-PW9O34)] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.展开更多
Crystal of H14C[A-β-SiW9Al3(H2O)2O36(μ3-O2/2)]2 ·8H2O belongs to monoclinic system, space group P2/m. with a= 1 7. 525(6), b=14.348(3). c= 21. 669(8) A , β=113. 12(8)°, V = 5011 (3) A3,Z = 2. Dc = 3. 254 ...Crystal of H14C[A-β-SiW9Al3(H2O)2O36(μ3-O2/2)]2 ·8H2O belongs to monoclinic system, space group P2/m. with a= 1 7. 525(6), b=14.348(3). c= 21. 669(8) A , β=113. 12(8)°, V = 5011 (3) A3,Z = 2. Dc = 3. 254 g. cm-3, A (MoKα) = 0. 70169 A , μ=223. 21 cm-1, F(000) = 4614, T = 298K. R=0. 066 for 3010 unique reflections [I≥5σ(I) ]. The crystal consists of water molecules, protons (or H3O+ ) and dimeric anions [A-β-SiW9Al3 (H2O)2O36(μ3-O2/2)D214.the half of which has a SiO1 tetrahedron in the center, a W3O13 group, two W2Al(H2O) O12 groups and a W2AlO13 group around the SiO4.展开更多
Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent hete...Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.展开更多
Direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide over Co1.5PW12O40 in liquid and in gas phase is investigated. The synthesized catalyst has been characterized by means of FTIR and XRD. L...Direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide over Co1.5PW12O40 in liquid and in gas phase is investigated. The synthesized catalyst has been characterized by means of FTIR and XRD. Liquid phase experiment results showed that high pressures are favorable for the synthesis of DMC. However, DMC formation is limited by the reaction with co-produced water. DMC selectivity is more strongly dependent on the temperature than on the pressure of CO2. As for the reactions in gas phase, it has been found that both CH3OH conversion and DMC selectivity decreased with increasing temperature, owing to the decomposition of DMC at high temperatures. High temperatures and more amount of Co1.5PW12O40 catalyst favor the formation of dimethoxymethane (DMM) and methyl formate (MF).展开更多
Undecatungstocobaltoruthenic polyoxometallic acid H7[Ru(H2O)CoW11O39] 22H2O was synthesized by the stepwise acidification and the stepwise addition of solutions of the component elements as well as the ion ex changi...Undecatungstocobaltoruthenic polyoxometallic acid H7[Ru(H2O)CoW11O39] 22H2O was synthesized by the stepwise acidification and the stepwise addition of solutions of the component elements as well as the ion ex changing-cooling method. The optimal proportion of the component compound and the pH of the synthesis reaction were given. The product was characterized by means of inductively coupled plasma(ICP), IR, UV and thermal analy sis. The IR and UV results indicate that H7[Ru(H2O)CoW11O39] 22H2O possesses the Keggin structure. The results of AC impedance measurement show that its proton conductivity is 2.30×10-3 S/cm at room temperature(295 K) and a relative humidity of 75%.展开更多
The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution...The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution of the component elements. The products werecharacterized by ICP, IR, UV, XRD and TG-DTA. The proton conductibility and the activation energy ofproton conduction of the heteropoly acids were investigated.展开更多
基金This work was supported by the National Natural Science Foundation of China, Specialized Research Fund for the Doctoral Program of Higher Education, Henan Innovation Project for University Prominent Research Talents, Program for New Century Excellent Talents in Universities of Henan Province, the Foundation of Educational Department of Henan Province and Natural Science Foundation of Henan Province
文摘A novel polyoxometalate-based composite compound [Ni(phen)2][Hphen](AsW12040) (phen = 1,10-phenanthroline) I has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, ESR spectroscopy and single-crystal X-ray diffraction. Each structure unit of 1 consists of one polyoxoanion AsW12O40^3-, one free phenanthroline molecule and one coordination cation [Ni(phen)2]^2+. The title compound crystallizes in the orthorhombic system, space group F212121, with a = 12.2383(7), b = 21.0884(11), c = 22.3237(12) A, V= 5761.4(5) A^3, Mr = 3520.44, Z = 4, Dc = 4.059 g/cm^3, F(000) = 6204, g(MoKα) = 24.844 mm^-1, GOF = 1.022, the final R = 0.0376 and wR = 0.0742 (I 〉 2σ(I)) for 865 parameters and 9637 observed reflections with I 〉 2σ(I).
文摘A new heteropolycomplex, K 6H 3[ZnW 11 O 40 Al]·9 5H 2O was prepared and characterized by means of elemental analysis, IR, UV spectroscopy, 27 Al NMR , electrochemistry and X ray crystallography. The crystal of K 6H 3[ZnW 11 O 40 Al]·9 5H 2O is cubic, space group Fm 3m , with lattice constants a=b=c =2 144 8(2) nm, V =9 866(2) nm 3, Mo radiation, R =0 057 8 for 497 independent data with [ I>2δ(I) ]. The anion is of α type Keggin structure with C s symmetry.
文摘For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated by means of polarograms,cyclic voltammetry,31P NMR and X-ray diffraction methods.The heteropolynier of PMo12 and AsMo12 converte to their β-isomers during isomerization reaction which were found to have antiacidolysis property.
文摘Two charge-transfer complexes of 2a and 2b of Keggin type were synthesized and characterized by elemental analysis, IR spectra, UV spectra, XRD, TG-DSC; and were compared with Hquin-PW12. The primary structure of the heteropolyanions had not been changed after the formation of the charge transfer complexes.
基金the NNSFC(21473030,1371033)Fujian Provincial Natural ScienceFoundation(2013J01042)the Open Fund of State Key Laboratory of Structural Chemistry(20130015)
文摘In this paper,One novel Keggin type polyoxomolybdate compounds have been hydrothermal synthesized:{[(CH3)2NH2]4(SiMo12O40)}[(CH3)2NH]·(DMF)0.5(1).The compound 1have been characterized by infrared spectrum,and the two-dimensional infrared correlation spectroscopy.
文摘The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic system with space group P , Mr=2117.73, a= 13.702(4), b=14.107(3), c=14.184(2) ; α=119.27(1), β=93.14(2), ;γ=110. 3(2)°, V=2154.29~3, Z=2, F(000)=1999, μ=36.39cm^(-1), Dc=3.26 g/cm^3. Final R factor is 0.0515. Mo(Ⅴ) is situated in two different edge-shared Mo_3O_(13) groups. The heteropoly blue was characterized by IR, UV, polarography, X-ray photoelectron spectra and ESR. All the results show that the structure of the heteropoly anion with Keggin structure remains unchanged basically in the process of reduction.
基金This work was supported by the National Natural Science Foundation of China, Specialized Research Fund for the Doctoral Program of Higher Education, Henan Innovation Project for University Prominent Research Talents, Program for New Century Excellent Talent in University of Henan Province, the Foundation of Educational Department of Henan Province and Natural Science Foundation of Henan Province
文摘A cobalt paradodecatungstate [Co(H2O)5]2[Co(H2O)4]3[H2W12O42]·11H2O has been successfully synthesized and structurally characterized by X-ray crystallography. Structure analysis indicates that the title compound is of monoclinic, space group P21/n, with a = 13.449(3), b = 19.585(4), c = 13.990(3) °A, = 113.79(3)°, V = 3371.8(12) °A^3, Z = 2, R = 0.0519 and wR = 0.1242. The title compound exhibits a novel 3D extended network structure constructed by interconnecting the paradodecatungstate polyanion [H2W12O42]^10- clusters and cobalt^11 coordination ions.
基金the National Natural Science Foundation for Distinguished Young Scholars, 973 Program (No. 2006CB932900)NNSFC (No. 20473090)+1 种基金NSF of Fujian Province (No. E0510030)Key Project from CAS (No. KJCX2.YW.H01)
文摘Three new inorganic-organic composite polyoxotungstates [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]-4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847(3), b = 21.597(2), c = 20.1179(19)A, V= 12099(2)A^3, Z= 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1^- with a = 12.31150(10), b = 16.1954(4), c = 19.36290(10)A, α = 99.366(11), β =105.168(8), γ = 111.836(8)°, V = 3309.98(9)A3, Z = l, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5)A, β = 102.338(5)°, V= 4103(2)A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1-3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.
基金Supported by the National Natural Science Fund for Distinguished Young Scholars of China (No. 20725101)the NNSFC (Nos. 50872133 and 20821061)+2 种基金the 973 Program (No. 2006CB932904)the NSF of Fujian Province (No. E0510030)the Knowledge Innovation Program of CAS
文摘Two new hybrid polyoxotungstates, [Co(2,2'-bipy)3][a-H5PW11CoO40]-3H2O 1 and [Fe(2,2'-bipy)3]2[a-HBW12O40]-2.5H2O 2 (2,2'-bipy = 2,2'-dipyridyl), have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co(2,2'-bipy)3]2+ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe(2,2'-bipy)3]2+ cations. The data for 1: orthorhombic system, space group Pbcn, a = 16.062(6), b = 27.278(10), c = 16.951(6)A, V = 7427(5)A3 and Z = 4; and those for 2: triclinic system, space group P1, a = 13.787(3), b = 17.857(5), c = 18.918(5)A, a = 88.009(12), β = 72.768(10), γ = 74.935(10)°, V = 4291(2)A3 and Z = 2.
基金financially supported by the National Natural Science Foundation of China (No. 2057023)the Program for New Century Excellent Talents in Universities of Henan Province (No. 2005HANCET)+2 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20040475001)Henan Innovation Project for University Prominent Re-search Talents (No. 2005KYCX011)the Natural Science Foundation of Henan Province, China (No. 0411051700)
文摘The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu(DMF)3(H2O)212[SiMo12O40].2H2O (DMF = N, N-dimethyl formamide) is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper(I/) centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.
文摘A new coordination compound, [{Nd(NMP)_2(H_2O)_6Cl}{Nd(NMP)_2(H_2O)_7}H (P_2Mo_(18)O_(62)) (NMP=N-methyl-2-pyrrolidone) was synthesized and characterized by elemental analyses, IR spectrum, and X-ray single crystal structural analysis. The crystal structure indicates that the title compound belongs to monoclinic space group C _c, with unit cell dimensions a =2.4528(5) nm, b =1.9495(4) nm, c =2.4405(5) nm, β =109.94(3)°, Z =4, V =10.970 (4) nm^3, D _c=2.262 g·cm^(-3), R 1=0.0676, wR 2=0.1441. The ESR spectrum of powder of the title compound at 110 K after being exposed to sunlight shows the signal of Mo^(5+), g =1.95. Cyclic voltammetry was measured in aqueous solution containing 0.1 mol·L^(-1) KCl as the supporting electrolyte and shows that the title compound undergoes two one-electron reversible reductions.
文摘A 1D chain-like organic-inorganic hybrid rare earth derivative of polyoxometalate H0.5[Sm(H2O)6]0.25[Sm(H2O)5]0.25{[Sm(H2O)7][Sm(H2O)2(DMSO)][SiW11O39]}·4.5H2O has been firstly synthesized by reaction of α-K8SiW11O39.13H2O, HClO4, Sm2O3 with dimethyl sulfoxide (DMSO) and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. The neighboring polyanionic units {[Sm(H2O)7][Sm(H2O)2(DMSO)][SiWHO39]}^2- are bridged together to a 1D chain structure by means of [Sm(H2O)2(DMSO)]^3+ ion.
基金The project was supported by the Natural Science Foundation of Henan Province (NO. 004040300) and the Outstanding Youth Foundation of Henan Province (NO. 004031800)
文摘A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(3), V = 1865.6(6) 3, Dc = 2.445 g/cm3, Z = 1, ?= 2.660 mm-1, Mr = 2746.56, F(000) = 1328, R = 0.0569, wR = 0.1190 and GOF = 1.125. The results of X-ray crystal analysis and IR spectrum show that there exists strong interaction between the heteropolyanions [SiMo12O40]4- and coordination cations [Mn(DMSO)5H2O]2+ in solid state.
基金Supported by the NNSF for Distinguished Young Scholars of China (No. 20725101)the 973 program (No. 2006CB932900)+2 种基金the NNSFC (No. 20521101)the NSF of Fujian Province (No. E0510030)Key Project from CAS (No. KJCX2-YW-H01)
文摘A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6(μ3- OH)3(en)3(H2O)6}(B-α-PW9O34)]-6H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis (TGA), single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124(5), c = 21.4427(4)A, γ = 120.000°, V = 7737.5(3)A3, Z = 6, GOF = 1.083, R (wR) = 0.0317 (0.0610). Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6(μ3-OH)3(en)3(H2O)6}(B-α-PW9O34)] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.
文摘Crystal of H14C[A-β-SiW9Al3(H2O)2O36(μ3-O2/2)]2 ·8H2O belongs to monoclinic system, space group P2/m. with a= 1 7. 525(6), b=14.348(3). c= 21. 669(8) A , β=113. 12(8)°, V = 5011 (3) A3,Z = 2. Dc = 3. 254 g. cm-3, A (MoKα) = 0. 70169 A , μ=223. 21 cm-1, F(000) = 4614, T = 298K. R=0. 066 for 3010 unique reflections [I≥5σ(I) ]. The crystal consists of water molecules, protons (or H3O+ ) and dimeric anions [A-β-SiW9Al3 (H2O)2O36(μ3-O2/2)D214.the half of which has a SiO1 tetrahedron in the center, a W3O13 group, two W2Al(H2O) O12 groups and a W2AlO13 group around the SiO4.
基金supported by the chemical materials institute China academy of engineering physics,the doctoral innovation research assistance program of science and technology review
文摘Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.
基金the Deanship of Scientific Research at King Saud University for funding the work through the research group project (No. RGP-VPP-116)
文摘Direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide over Co1.5PW12O40 in liquid and in gas phase is investigated. The synthesized catalyst has been characterized by means of FTIR and XRD. Liquid phase experiment results showed that high pressures are favorable for the synthesis of DMC. However, DMC formation is limited by the reaction with co-produced water. DMC selectivity is more strongly dependent on the temperature than on the pressure of CO2. As for the reactions in gas phase, it has been found that both CH3OH conversion and DMC selectivity decreased with increasing temperature, owing to the decomposition of DMC at high temperatures. High temperatures and more amount of Co1.5PW12O40 catalyst favor the formation of dimethoxymethane (DMM) and methyl formate (MF).
基金Supported by the National Natural Science Foundation of China(No.21071124)the Foundation of Jiangxi Education De-parment, China(No.GJJ09310)the Foundation of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, China(No.2010-16)
文摘Undecatungstocobaltoruthenic polyoxometallic acid H7[Ru(H2O)CoW11O39] 22H2O was synthesized by the stepwise acidification and the stepwise addition of solutions of the component elements as well as the ion ex changing-cooling method. The optimal proportion of the component compound and the pH of the synthesis reaction were given. The product was characterized by means of inductively coupled plasma(ICP), IR, UV and thermal analy sis. The IR and UV results indicate that H7[Ru(H2O)CoW11O39] 22H2O possesses the Keggin structure. The results of AC impedance measurement show that its proton conductivity is 2.30×10-3 S/cm at room temperature(295 K) and a relative humidity of 75%.
文摘The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution of the component elements. The products werecharacterized by ICP, IR, UV, XRD and TG-DTA. The proton conductibility and the activation energy ofproton conduction of the heteropoly acids were investigated.