Synthesis and Crystal Structure of a Polyoxomolybdate Framework Modified by Mn-L Units(L=3-(2-Pyridyl)pyrazole)

A new polyoxomolybdate compound,namely {[MnII（L）（4,4？-Hbipy）（H2O）2]2 [Mo5O15（PO4）2]}.2H2O 1（L = 3-（2-pyridyl）pyrazole,4,4＇-Hbipy = protonated 4,4＇-bipyridine）,was designed and synthesized under hydrothermal conditions.Single-crystal X-ray diffraction analysis result reveals that the [Mo5O15（PO4）2]6-cluster in compound 1 links to two MnII cations via the oxygen of PO43-,which is further coordinated by one 3-（2-pyridyl）pyrazole,one 4,4＇-Hbipyridine,and two water molecules.

1-Methyl-3-octylimidazolium Polyoxomolybdate Ionic Liquid with Low Melting Point and High Stability:Preparation and Photocatalytic Activity

The polyoxometalate（POM）-imidazole ionic liquid（IL） [C8mim]2[Mo6O19]（C8mim=1-methyl-3-octylimi- dazolium） with a low melting point of 82.6 °C was successfully prepared and characterized by FTIR, XPS, NMR, TG and so on. The polyoxomolybdate-based IL has high stability, and its decomposing temperature reaches 321 °C, which is higher than that of 1-alkyl-3-methylimidazolium halides IL. Further photocatalytic performances of the IL were measured via degrading dye rhodamine B（RB） in aqueous solution under the UV light irradiation. The experiments show that the conversion of RB reaches 80.5% after 90 min under UV-light and the degradation efficiency depends on the pH value of the solution, irradiation time and the dosage of the IL and so on.

Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [{Na(H_2O)_3}_2{Ru(dmso)_3}_2(MoO_4)_3]·_3H_2O

The title compound, [{Na（H2O）3}2lRu（dmso）3}2（MoO4）3]·3H2O, has been obtained by the reaction of Na2MoO4·2H2O with cis-Ru（dmso）4Cl2 in aqueous solution. Its crystal structure was determined by single-crystal X-ray diffraction method. The crystal crystallizes in the triclinic system, space group PI^- with a = 12.3333（3）, b = 12.6289（3）, c = 32.0284（14） A, α = 79.873（7）, β= 87.549（9）, γ = 64.500（4）°, V = 4429.5（2） A^3, Z = 4, Mr = 1358.85, Dc = 2.038 g/cm^3, F（000） = 2696 and μ = 1.874 mm^-1. The compound contains a novel pentanuclear triangle bipyramidal core, [{ Ru（dmso）3 } 2（MoO4）3]^2-, which consists of two { Ru（dmso）3 } ^2＋ fragments and three {μ2-MoO4}^2- units. Furthermore, the dmso ligands bridge the pentanuclear [Ru2Mo3] core and two [Na（H2O）3]^＋ fragments together, forming a neutral heptanuclear ruthenium- and sodiumcontaining polyoxomolybdate.

Synthesis and Structural Characterization of Manganese Carbonyl Incorporated Polyoxomolybdate (n-Bu_4N)_2[Mo_6O_(16)(OCH_3)_2{HOCH_2C(CH_2O)_3}_2{Mn(CO)_3}_2]

The polyoxoanion incorporated {Mn（CO）3^＋} complex, （n-Bu4N）2[Mo6O16（OCH3）2{HOCH2C（CH2O）3}2·{Mn（CO）3}2]（1）, has been synthesized by the reaction of （n-Bu4N）4[Mo8O26] with Mn（CO）5Br in methanol, in the presence of C（CH2OH）4. The complex 1 has been characterized by IR, UV-Vis, X-ray single crystal diffraction, and TG. Crystal data for the complex 1：C25H48MnMo3NO16 （1）, Triclinic Pi, a=0.9405（3） nm, b=1.3351（4） nm, c=1.5455（4） nm, α=103.206（5）°, β=102.165（5）°, γ=100.784（5）°, V=1.7896（9） nm^3, Z=2, R1=0.0703, wR2= 0.1495. The structure analysis of complex 1 shows that the complex consists of two tetrabutylammonium cations and a polyoxomolybdate anion that incorporates two fac-Mn（CO）3^＋ units. The anion of complex 1 can be considered as the dimer of two rhomb-like anions by sharing of two comers.

Synthesis and Structural Characterization of a Polyoxomolybdate HNa_7[Mo_(36)O_(112)(H_2O)_(16)]·47H_2O

A new polyoxomolybdate complex HNaT[Mo36O112（H2O）16]·47H2O 1 has been prepared in the beaker solution and characterized by single-crystal X-ray diffraction and elemental analyses. Crystal data： H127Mo36Na7O175, Mr = 6542.79, monoclinic, C2/c, a = 40.891（6）, b = 17.900（3）, c = 25.580（4）A, β = 125.673（2）°, V = 15210（4）A3, Z = 4, Dc = 2.857 g/cm^3, F（000） = 12464,μ = 3.013 mm^-1, R = 0.0633 and wR = 0.1654 （I 〉 20（I））. With the bridging sodium cations, the [Mo36Ou2（H2O）16]^8- units in compound 1 are linked to form a one-dimensional structure, on the basis of which a three-dimensional architecture is further constructed via other sodium cations and complicated hydrogen bonds.

Structures and Spectroscopy Properties of One Novel Keggin Type Polyoxomolybdate Compound

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.

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates：[Cu^Ⅱ2（HL）3]2[Mo8O26）]·（H2O）4 and [Ni^Ⅱ（HL）3]2（Mo8O26）·（H2O）3（HL=3-（2-Pyridyl）pyrazole）

Two new polyoxomolybdate compounds,namely CuII2（HL）3]2[Mo8O26]·（H2O）4（1） and [NiII（HL）3]2（Mo8O26）·（H2O）3（2）（HL = 3-（2-pyridyl）pyrazole）,were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu（II） ions linked by three 3-（2-pyridyl）pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-（2-pyridyl）pyrazole ligands.Crystal data of 1：C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850（2）,b = 18.510（4）,c = 17.230（3） ,β = 100.57（3）°,V = 3401.6（12） 3,Z = 4,Dc = 2.324 g/cm3,F（000） = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775（Ⅰ 〉 2σ（Ⅰ））;Crystal data for 2：C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799（2）,b = 14.7970（13）,c = 23.141（2） ,β = 91.6180（10）°,V = 7119.0（11） 3,Z = 4,Dc = 2.077 g/cm3,F（000） = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696（Ⅰ〉 2σ（Ⅰ））.

Hydrothermal syntheses and structural characterizations of three polyoxomolybdates frameworks linked by M(HL)_2 units(M=Co,Ni,Zn;L=3-(2-pyridyl)pyrazole)

Three polyoxomolybdate compounds,namely {[MII(HL)2]2(Mo8O26)}n(M = Co(1),Ni(2),Zn(3))(HL,3-(2-pyridyl)pyrazole),were designed and synthesized under the hydrothermal conditions and characterized by elemental analysis,IR spectroscopy,and TGA.Single-crystal X-ray diffraction analysis results reveal that compounds 1-3 own the isostructural chain structure consisting of the β-[Mo8O26]4- anions,which are linked by M(HL)22+ units via the terminal oxygen atoms.TGA curves show that the organic ligands separate from the related compounds above ca.673 K.

Synthesis and Structural Characterization of Three New Inorganic “Host-guest”Polyoxomolybdates

Since two interesting inorganic “host guest” polyoxomolybdates 1 and 2 have been reported previously, we have now succeeded in selectively isolating three new acetated “host guest” polyoxomolybdates 3—5, which considerably extend the range of structures in the cyclic polyoxomolybdate catalogue. 3 crystallizes in the triclinic space group P 1 with a =1 22235(1) nm, b =1 52977(2) nm, c =1 54022(1) nm, α =113 746(1)°, β =96 742(1)°, γ = 101 564(1)°, V =2 51892(4) nm 3, Z =1, D c=2 568 g·cm -3 . 4 and 5 crystallize in the monoclinic system: P 2(1)/ n , a =1 08298(2) nm, b =1 54029(1) nm, c = 2 78893(5) nm, β =94 2730(10)°, V =4 63929(12) nm 3, Z =2 and D c=2 671 g·cm -3 for 4, and C 2/ c , a =2 59907(8) nm, b =1 65992(3) nm, c =2 28473(7) nm, β = 93 4370(10)° , V =9 8392(5) nm 3, Z =4 and D c=2 556 g·cm -3 for 5. The structures of 3, 4 and 5 consist of 18 membered “host guest” polyoxoanions [{Na(X) 2}{( μ 3 OH) 4Mo V 8Mo VI 10 O 52 ( μ 2 CH 3COO) 2}] -( n +9) (X=CH 3COO - for 3, DMF for 4 and H 2O for 5), which are connected via Na + ions or hydrogen bonds into infinite extended frameworks.

Synthesis and Crystal Structure of［（n－Bu）_4N］_2［Mo_4O_（10）（OC_（10）H_6O）_2（OCH_3）_2］

n-Bu )_4N]_2 [Mo_4O_(10) (OC_(10)H_6O)_2 (OCH_3 )_2 ] crystallizes in the monoclinic, space group P21/c, a= 10. 926 (6) , b= 17. 861 (7) . c= 16. 258 (7) ,β=91. 16(4)°, V= 3172 (2) ￣3, Z = 2, M_r = 1407. 0, D_c =1. 473 g/cm￣3 , μ= 0. 814mm￣(-1), F(000) = 1448. T= 298K , final R= 0. 043 and R_w= 0. 058 for 3291 observed reflections. The structure of the complex consists of two (n-Bu)_4N￣+ cations and one [Mo_4 O_(10) (OC_(10)H_6O)_2 (OCH_3 )_2]￣(2-) anion having crystallographic C_i symmetry, with a tetranuclear core of [Mo_4 O_(10)(OCH_3 )_2]￣(2+) .

A Two-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Ag(Ⅰ)-[3-(2-pyridyl)-pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Ag 3 （HL） 4 ]（PMo 12 O 40）] 1 （HL=3-（2-pyridyl）pyrazole） has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.375（3）,b=12.076（3）,c=13.196（4）,α=84.170（4）,β=71.961（3）,γ=86.326（4）°,V=1563.1（7）3,C 32 H 28 Ag 3 Mo 12 N 12 O 40 P,M r=2726.52,D c=2.897 g/cm 3,μ（MoKα）=3.366 mm 1,F（000）=1284,Z=1,the final R=0.0587 and wR=0.1312 for 4139 observed reflections （I 2σ（Ⅰ））.X-ray diffraction analyses reveal that the PMo 12 O 40 3clusters in compound 1 are linked by four Ag 3 （HL） 4 3＋ units via the terminal oxygen atoms to form a two-dimensional architecture.The symmetrical unit of Ag 3 （HL） 4 3＋ exhibits two distinct Ag（Ⅰ） environments：a two-coordinate {AgN 2 } site and a five-coordinate {AgN 3 O 2 } site which links to two molybdate clusters.

A Two-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Zn(Ⅱ)-[3-(2-pyridyl)pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Zn（HL）2（Mo8O26）（4,4＇-Bipy）]·（4,4＇-Bipy） （HL = 3-（2-pyridyl）pyrazole, 4,4＇-Bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, TG and IR spectroscopy. The compound crystallizes in monoclinic, space group C2/c with a = 18.060（4）, b = 13.870（3）, c = 19.360（4） A, β = 93.50（3）°, V = 4840.5（17） 3, C36H30Mo8N10O26Zn, Mr = 1851.59, Dc = 2.541 g/cm^3, μ（MoKα） = 2.589 mm·1, F（000） = 3560, Z = 4, the final R = 0.0328 and wR = 0.0870 for 4005 observed reflections （I 〉 2σ（I））. X-ray diffraction analyses reveal that compound 1 is constructed from Mo8O264-units linked by Zn（HL）22＋ and 4,4＇-Bipy. Mo8O264-is connected by Zn（HL）2^2＋ via terminal oxygen atoms along the [010] axis forming chains, which are further linked by 4,4＇-Bipy along the [001] axis forming a two-dimensional network structure.

A New One-dimensional Chain Compound Constructed by {Mo_8O_(28)} units via Corner-sharing

The title compound, {(H3O)4(NH4)4[Mo8O28]?2H2O}n 1, has been synthesized from the reaction of Zn(OAc)2 and (NH4)6Mo7O24?4H2O in aqueous solution at ambient tempe- rature, and its crystal structure was determined by X-ray single-crystal analysis with the following crystallographic data: monoclinic system, space group P21/n, a = 9.5234(6), b = 11.3235(8), c = 14.8812(10) ?, β = 107.467(2)o, V = 1530.77(18) ?3, Z = 4, F(000) = 1336, μ = 3.293 mm-1 and Dc = 3.037 g/cm3. The final R = 0.0619 for 2691 observed reflections (I > 2σ(I)). X-ray crys- tal structure analysis showed that the novel one-dimensional chain compound is built up by basic {Mo8O28} units via single μ2-O, and such chains are further linked into a three-dimensional net- work by hydrogen bonds.

FORMATION OF MOLYBDENUM OXIDE NANOSTRUCTURES CONTROLLED BY POLY(ETHYLENE OXIDE)

Polymeric systems have played an important role as structure-directing agents and in the control of nucleation and growth of crystals.This article reviews the work of our research group in the field of the polymer-assisted crystallization of inorganic materials,mainly focused on the formation of highly ordered,porous molybdenum oxide nanostructures.Different experimental parameters including the influence of poly(ethylene oxide)-containing polymers on the morphology and structure of the products obtained fr...

Synthesis, Structure, and Magnetic Properties of One Polyoxometalate (W/Mo) Compound: H_8K{[Ni(H_2O)_5]_2(H_2Mo_(1.80)W_(10.20)O_(42))}Cl_3·16H_2O

One new polyoxometalate compound connected via nickel/potassium cations, H8K{[Ni（H2O）5]2（H2Mo1.80W10.20O42）}Cl3·16H2O 1, was prepared and characterized by elemental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis results reveal that clusters of [Ni（H2O）5]2（H2Mo1.80W10.20O42）}^6-in compound 1 are linked by potassium cations to form one- dimiensional chains, based on which a three-dimensional network is further constructed via the hydrogen bonds of O…O and O…Cl. Magnetic measurements show that compound 1 has paramagnetic properties. Crystal data： H62Cl3KMo1.80Ni2O68W10.20, Mr = 3461.33, monoclinic, space group C2/c, a = 18.9291（19）, b = 16.6758（17）, c = 19.1064（19）A, β = 106.6880（10）°, V = 5777.1（10）A^3, Z = 4, Dc = 3.980 g/cm^3, F（000） = 6250, μ = 21.574 mm^-1, R = 0.0579 and wR = 0.1623 （Ⅰ 〉 2σ（Ⅰ））.

A Novel Three-dimensional Inorganic Open-framework Constructed from [Mo_4O_(16)]_n ^(8n-) Chains Linked through Ag^+

A novel 3-D inorganic bimetallic compound Ag2Mo2O7 has been hydrothermally synthesized and structurally characterized by X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 6.1274（3）, b = 13.1836（6）, c = 7.8780（3）A, β= 110.673（3）°, V = 595.42（5）A3, Z= 4, Mr= 519.62, Dc = 5.797g/cm^3, F（000） = 936,μ（MoKα） = 10.579 mm^-1, F（000） = 936, the final R = 0.0204 and wR = 0.0477 for 1268 observed reflections with I〉 2σ（I）. In the title compound, the [Mo4O16]n^8n-chains are linked through O-Ag-O bridging bonds to form a 3D network. It represents an unprecedented linking mode between the isopolyoxomolybdate chain and the transition metal oxide cluster. IR, TGA and fluorescence properties of the title compound are also studied.

A New 3-D Network Based on Large Mo_(18)-Polyoxometalate Anionic Units and Alkaline Cations

The new polyoxomolybdate I was prepared from an aqueous solution by the reaction of Na2MoO4·H2O, NH2NH2·2HCl and HCOONa, and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray structural analysis. Crystal data： C4H72ClMo18Na13O94, Mr= 3685.86, triclinic, space group PI, a = 11.922（5）, b = 15.003（5）, c = 15.171（5） A, a = 116.073（5）, β = 112.593（5）, γ = 93.342（5）°, V= 2164.3（14） A^3, Z = 1, Dc = 2.828 g/cm^3, F（000） = 1764, p = 2.741 mm^-4, R = 0.0349 and wR = 0.0875 （I 〉 20（I））. X-ray crystal structure analysis shows that 1 is constructed by Mo18 polyoxoanions linked by Na^＋ cations to form a fascinating 3D open framework with ＂guest＂ Na^＋ cations and fonnyl groups residing in the channels.

Syntheses and Crystal Structures of two Ring-like {Mo_(18)} Cluster Compounds

Sodium molybdate was reduced to produce ring-like compounds in the presence of carboxylic acids. Compound 1: Na8(H2O)28(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(CH3C- OO)2]}11H2O (C8H103O102Na9S2Mo18, Mr = 3829.85), where the {Mo18} ring is built up by two acetic acids connecting two {Mo9} building blocks and the 1-D chain of 1 is formed through the coordinated sodium cations. Crystal data: triclinic, space group P, a = 11.3228(2), b = 15.4170(2), c = 16.7209(3) ? a = 113.006(1), b = 108.455(1), g = 92.430(1), V = 2501.98(7) 3, Z = 1, Dc = 2.542 g/cm3, F(000) = 1854, (MoKa) = 2.381 mm-1, T = 293(2) K, final R = 0.0532 and wR = 0.1203 for 7291 observed reflections with I > 2(I) from 8775 independent reflections. Compound 2: Na8(H2O)22(H3O)+{Na(DMSO)2[MoVI10MoV8O52(OH)4(C2H5COO)2]}10H2O (C10H93O94Na9- S2Mo18, Mr = 3715.79). Crystal data: monoclinic, space group C2/m, a = 18.044(1), b = 25.944(2), c = 10.4087(6) ? b = 106.613(2), V = 4669.3(5) 3, Z = 2, Dc = 2.643 g/cm3, F(000) = 3584, (MoKa) = 2.542 mm-1, T = 293(2) K, final R = 0.0536 and wR = 0.1621 for 4617 observed reflections with I > 2(I) from 5398 independent reflections. Similar to 1, the {Mo18} ring is built up by two {Mo9} building blocks that are connected up by two propanoic acids and these {Mo18} rings are further linked into a two-dimensional layer through the coordinated sodium cations.

Syntheses and Crystal Structures of Two Octamolybdate Compounds Modified by Cu~Ⅱ-Imidazole Cations

Two new polyoxomolybdate compounds,namely（CuIIL2）2[CuⅡ（HL）2]2[Mo8O26（HL）2].（H2O）4（1） and [CuⅡ（HL）2]2[β-Mo8O26]（HL）2（2）（HL=imidazole）,were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one Mo8O26（HL）24-cluster,two CuL2,two Cu（HL）22＋,and four disassociated water molecules;and compound 2 is constructed by one β-Mo8O264-cluster,two Cu（HL）22＋,and two uncoordinated imidazole molecules.

A One-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Mn(Ⅱ)-[3-(2-pyridyl) pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Mn II （L） 2 （Mo 8 O 26） 0.5 ] 2n （1,L=3-（2-pyridyl）pyrazole） has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in the triclinic system,space group P1 with a=10.063（4）,b=11.554（5）,c=11.554（5）,α=88.89,β=74.839（4）,γ=74.839（4）o,V=1249.8（9） 3,C 16 H 14 MnMo 4 N 6 O 13,M r=937.03,D c=2.490 g/cm 3,μ（MoKα）=2.521 mm 1,F（000）=898,Z=2,the final R=0.0390 and wR=0.0970 for 4000 observed reflections （I 2σ（Ⅰ））.Single-crystal X-ray diffraction analysis results reveal that compound 1 owns a chain structure based on β-[Mo 8 O 26 ] 4anions,which are linked by Mn II （L） 2 units via the terminal oxygen atoms.