The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a=...The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm3, Z=2, Dc=2.388g·cm-3, Mr=2465.10g·mol-1, μ=2.489mm-1, F(000)=2388, R1=0.0584, wR2=0.1461, S=1.164. The heteropolyanion is a bi capped pseudo Keggin complex. CCDC: 186645.展开更多
A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-cry...A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system with a = 11.927（2）, b = 13.328（3）, c = 19.306（4）A, a = 93.76（3）, β = 94.14（3）, γ = 109.99（3）°, V= 2863.2（12） A3, space group P1 and Z = 2 at 173 K. The final full-matrix least-squares refinement converged to R = 0.049 for 9621 observed reflections with 1 〉 2σ（I） and wR = 0.139 for all data （9871） and S = 1.073. Crystal structure analysis shows that 1 contains a kind of the first reported mixed-valence and molybdenum-tungsten mixed-distributed e-Keggin structural polyanion capped by four Co（dien） fragments with the main group element P occupying the center site. These results were further confirmed by energy-dispersive X-ray spectroscopy （EDS）, X-ray powder diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR）, Raman spectroscopy, Thermogravimetry （TG） and X-ray photoelectron spectroscopy （XPS） analyses.展开更多
The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compou...The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- guest.展开更多
Polyoxometallates Co(en) 3PMo 12O 40·8H 2O(+,-)[abbreviated as PMo 12-Co(+,-)], nanoparticles were synthesized by the chemical precipitation reaction at room temperature for the first time. They were c...Polyoxometallates Co(en) 3PMo 12O 40·8H 2O(+,-)[abbreviated as PMo 12-Co(+,-)], nanoparticles were synthesized by the chemical precipitation reaction at room temperature for the first time. They were characterized by means of elemental analyses, IR spectrometry and X-ray diffraction. The images of scanning electron microscopy(SEM) and the results of calculation by using the Scherrer equation for the line widths of the XRD patterns were used to estimate the average particle size of the powder products, which was 40 nm. The results show that the nanoparticle size was affected by starting materials′ concentrations. The particles had a small size and a narrow distribution, when the concentrations of H 3PMo 12O 40·24H 2O and Co(en) 3I 3·H 2O were around 1.7×10 -4 and 1.0×10 -3 mol/L, respectively. When the concentration was increased, there was no significant increase in the particle size, but more polydisperse Co(en) 3(PMo 12O 40) (+, -) were obtained. In poly(ethylene glycol)(PEG) with an average molecular weight(M W) of 600 g/mol and containing LiClO 4[n(O)/n(Li)=100∶1] as the supporting electrolyte, the conductivity of the composite system increases upon the addition of PMo 12-Co(+ or -) nanoparticles, which was measured by the a.c. impedance technique. The interactions among PEG, LiClO 4, PMo 12, and Co can be used to explain that the PMo 12-Co(+ or -) nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.展开更多
SCC-DV-X method was used for the theoretical calculation of heteropoly an- ion , [SiMoO40]4- . and heteropoly blue anions,[SiMo2 Mo10O40]6 and [SiMo4 Mo!; O' 1,-. Th. f.o.ti.. .ol...l.. orbital. , orbital e.e.gi....SCC-DV-X method was used for the theoretical calculation of heteropoly an- ion , [SiMoO40]4- . and heteropoly blue anions,[SiMo2 Mo10O40]6 and [SiMo4 Mo!; O' 1,-. Th. f.o.ti.. .ol...l.. orbital. , orbital e.e.gi.. , Fe.mi 1...l. , the o.- cupied numbers of basis functions , free valences , Mulliken populations and the fig- ure of the total density of states have been obtained. The theoretical analysis indi- cates that all the atoms in the anions participate in chemical reactions , but Oc and Od have higher chemical activities than other atonts , which is supported by the ex- perimental results. The heteropoly hue anions with the α-Keggin structure distort a little and the levels of valence orbitals demonstrate that [SiMo4 Mo8O40]8 can form a six-electron heteropoly blue anoint by accepting two electrons.展开更多
Potassium tetraniobooccatungotosilicate, K8 [SiNb4 W8 O40] · 12H2 O was pre-pared by the reaction of white powdery tungstic acid, potassium niobate and potas -sium silicate in aqueous solution ...Potassium tetraniobooccatungotosilicate, K8 [SiNb4 W8 O40] · 12H2 O was pre-pared by the reaction of white powdery tungstic acid, potassium niobate and potas -sium silicate in aqueous solution with pH value adjusted by potassium carbonate。The heteropolyniobotungstate crystallized in cubic space group Pm3m with unit cellparameters ;: a = 1.0640(1)nm,Z=1,V=1 .2045(5)nm3,R=0.055,Rw =0.062。The anion has inverse,Keggin structure,in which the central SiO4 tetrahedron isdistributed statistically in two orientations。The twelve outer metal positions arerandomly occupied by four niobium and eight tungsten atoms. Moreover, infraredspectrat electronic :spectra and thermogram were measured。展开更多
The title compound, (H2en)3H3O{Mo8V4O36(VO4) (VO)2} ?4H2O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclin...The title compound, (H2en)3H3O{Mo8V4O36(VO4) (VO)2} ?4H2O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclinic system with space group P21/c, a=1. 980 4(4) nm, 6=2. 063 4(4) nm, c=l. 192 0(2) nm, =94. 76(3)?and deep black colour. The compound contains V-centered bi-capped a-Keggin fragments {Mo8V7O42} that are linked together by edge-shared units V O5 via V桹梀 bonds, forming a chain.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
A new pseudo Keggin-type bicapped compound（Et3N）0.5（en）2[SiMo12O40（VO）2]·4H2O（Et3N=triethylamine,en=ethylenediamine） has been hydrothermally synthesized and characterized by IR,elemental analysis,TG and X...A new pseudo Keggin-type bicapped compound（Et3N）0.5（en）2[SiMo12O40（VO）2]·4H2O（Et3N=triethylamine,en=ethylenediamine） has been hydrothermally synthesized and characterized by IR,elemental analysis,TG and X-ray crystallography.The title compound crystallizes in monoclinic,space group P21/n with a=17.576（2）,b=13.535（1）,c=21.587（2）,β=103.790（10）°,V=4987.3（8）3,Z=4,Dc=2.925 Mg/m3,Mr=2196.12,F（000）=4148,μ=3.400 mm–1,R=0.0379 and wR=0.1219.The most remarkable structural feature of the compound is that the clusters represent bicapped pseudo-Keggin structure and are linked one by one through V-O-V bonds forming an infinite 1D chain. Furthermore, such chains are interconnected in a cross-like arrangement through multiform hydrogen bonds to yield a 3D supramolecular network.展开更多
文摘The novel polyoxometalate, 32[Mo8ⅣMo4ⅤV2ⅣO38(PO4)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X ray diffraction. The compoundcrystallizes in triclinic system, space group with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm3, Z=2, Dc=2.388g·cm-3, Mr=2465.10g·mol-1, μ=2.489mm-1, F(000)=2388, R1=0.0584, wR2=0.1461, S=1.164. The heteropolyanion is a bi capped pseudo Keggin complex. CCDC: 186645.
基金Foundation of Education Department of Fujian Province(Nos.JA11245 and JB12199)National Natural Science Foundation of China(No.40972035)
文摘A novel inorganic-organic hybrid compound, {[Co（dien）]4[0aO4）MoV8（wV10.56MoV10.44）4- O33（OH）3]}＇nH20 （1, n = 1, dien = diethylenetriamine）, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system with a = 11.927（2）, b = 13.328（3）, c = 19.306（4）A, a = 93.76（3）, β = 94.14（3）, γ = 109.99（3）°, V= 2863.2（12） A3, space group P1 and Z = 2 at 173 K. The final full-matrix least-squares refinement converged to R = 0.049 for 9621 observed reflections with 1 〉 2σ（I） and wR = 0.139 for all data （9871） and S = 1.073. Crystal structure analysis shows that 1 contains a kind of the first reported mixed-valence and molybdenum-tungsten mixed-distributed e-Keggin structural polyanion capped by four Co（dien） fragments with the main group element P occupying the center site. These results were further confirmed by energy-dispersive X-ray spectroscopy （EDS）, X-ray powder diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR）, Raman spectroscopy, Thermogravimetry （TG） and X-ray photoelectron spectroscopy （XPS） analyses.
基金This work was supported by the Science and Technology Development Foundation of Fuzhou University (No.2004-xq-05)the Scientific Research Foundation of Fujian Provincial Education Department (No. JB04010)
文摘The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- guest.
基金Supported by the National Natural Science Foundation of China(No.2 0 3710 0 7)
文摘Polyoxometallates Co(en) 3PMo 12O 40·8H 2O(+,-)[abbreviated as PMo 12-Co(+,-)], nanoparticles were synthesized by the chemical precipitation reaction at room temperature for the first time. They were characterized by means of elemental analyses, IR spectrometry and X-ray diffraction. The images of scanning electron microscopy(SEM) and the results of calculation by using the Scherrer equation for the line widths of the XRD patterns were used to estimate the average particle size of the powder products, which was 40 nm. The results show that the nanoparticle size was affected by starting materials′ concentrations. The particles had a small size and a narrow distribution, when the concentrations of H 3PMo 12O 40·24H 2O and Co(en) 3I 3·H 2O were around 1.7×10 -4 and 1.0×10 -3 mol/L, respectively. When the concentration was increased, there was no significant increase in the particle size, but more polydisperse Co(en) 3(PMo 12O 40) (+, -) were obtained. In poly(ethylene glycol)(PEG) with an average molecular weight(M W) of 600 g/mol and containing LiClO 4[n(O)/n(Li)=100∶1] as the supporting electrolyte, the conductivity of the composite system increases upon the addition of PMo 12-Co(+ or -) nanoparticles, which was measured by the a.c. impedance technique. The interactions among PEG, LiClO 4, PMo 12, and Co can be used to explain that the PMo 12-Co(+ or -) nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.
文摘SCC-DV-X method was used for the theoretical calculation of heteropoly an- ion , [SiMoO40]4- . and heteropoly blue anions,[SiMo2 Mo10O40]6 and [SiMo4 Mo!; O' 1,-. Th. f.o.ti.. .ol...l.. orbital. , orbital e.e.gi.. , Fe.mi 1...l. , the o.- cupied numbers of basis functions , free valences , Mulliken populations and the fig- ure of the total density of states have been obtained. The theoretical analysis indi- cates that all the atoms in the anions participate in chemical reactions , but Oc and Od have higher chemical activities than other atonts , which is supported by the ex- perimental results. The heteropoly hue anions with the α-Keggin structure distort a little and the levels of valence orbitals demonstrate that [SiMo4 Mo8O40]8 can form a six-electron heteropoly blue anoint by accepting two electrons.
文摘Potassium tetraniobooccatungotosilicate, K8 [SiNb4 W8 O40] · 12H2 O was pre-pared by the reaction of white powdery tungstic acid, potassium niobate and potas -sium silicate in aqueous solution with pH value adjusted by potassium carbonate。The heteropolyniobotungstate crystallized in cubic space group Pm3m with unit cellparameters ;: a = 1.0640(1)nm,Z=1,V=1 .2045(5)nm3,R=0.055,Rw =0.062。The anion has inverse,Keggin structure,in which the central SiO4 tetrahedron isdistributed statistically in two orientations。The twelve outer metal positions arerandomly occupied by four niobium and eight tungsten atoms. Moreover, infraredspectrat electronic :spectra and thermogram were measured。
文摘The title compound, (H2en)3H3O{Mo8V4O36(VO4) (VO)2} ?4H2O, was hydrothermally synthesized and structurally characterized by means of IR, ESR spectrum and single crystal X-ray diffraction. It crystallized in a monoclinic system with space group P21/c, a=1. 980 4(4) nm, 6=2. 063 4(4) nm, c=l. 192 0(2) nm, =94. 76(3)?and deep black colour. The compound contains V-centered bi-capped a-Keggin fragments {Mo8V7O42} that are linked together by edge-shared units V O5 via V桹梀 bonds, forming a chain.
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.
基金supported by the National Natural Science Foundation of China (No 20701012)the Key Project of Chinese Ministry of Education (No 207068)+1 种基金the Foundation of Henan Educational Committee of China (No 2007150003 and 2008B150002)the Foundation for University Youth Key Teacher of Henan Province
文摘A new pseudo Keggin-type bicapped compound（Et3N）0.5（en）2[SiMo12O40（VO）2]·4H2O（Et3N=triethylamine,en=ethylenediamine） has been hydrothermally synthesized and characterized by IR,elemental analysis,TG and X-ray crystallography.The title compound crystallizes in monoclinic,space group P21/n with a=17.576（2）,b=13.535（1）,c=21.587（2）,β=103.790（10）°,V=4987.3（8）3,Z=4,Dc=2.925 Mg/m3,Mr=2196.12,F（000）=4148,μ=3.400 mm–1,R=0.0379 and wR=0.1219.The most remarkable structural feature of the compound is that the clusters represent bicapped pseudo-Keggin structure and are linked one by one through V-O-V bonds forming an infinite 1D chain. Furthermore, such chains are interconnected in a cross-like arrangement through multiform hydrogen bonds to yield a 3D supramolecular network.
