Synthesis and Spectroscopic Characterization of Organophosphoryl Polyoxotungstates α-A-[RP(O)]2PW9O5-34

Derivatized polyoxometalates(POMs), especially those including organic and organometallic components, have received current attention due to their potential application in catalysis, medicine and material sciences[1].     

Hydrothermal Synthesis and Structure of One New Polyoxotungsate [Ni(trien)]_4[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O

One new sandwich-type tetra-nickel substituted polyoxotungsate,[Ni(trien)]4-[Ni4(H2O)2(HPW9O34)2]·4H2O(1,trien=triethylenetetramine),has been hydrothermally synthesized and characterized by IR,elemental analysis,TGA,and single-crystal X-ray diffraction analysis.Crystal data for 1:triclinic,space group P with a=13.279(3),b=13.816(3),c=14.494(4),α=95.403(1),β=113.173(4),γ=93.809(3)o,V=2418.0(10)3,Z=1 and Dc=3.861 g/cm3.X-ray crystallographic study shows that compound 1 is a relatively rare inorganic-organic hybrid polyoxo tungstate constructed from sandwich Ni-substituted polyoxo-anions and nickel complexes.     

Hydrothermal Synthesis and Structure of One New Polyoxottmgsate [Ni(trien)]_4[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O

One new sandwich-type tetra-nickel substituted polyoxotungsate,[Ni(trien)]_4-[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O(1,trien=triethylenetetramine),has been hydrothermally synthesized and characterized by IR,elemental analysis,TGA,and single-crystal X-ray diffraction analysis.Crystal data for l:triclinic,space group Pī with a=13.279(3),b.13.816(3),C=14.494(4)(A),α=95.403(1),β=113.173(4),γ=93.809(3)°,V=2418.0(10)(A)~3,Z=1 and Dc=3.861g/cm~3.X-ray crystallographic study shows that compound 1 is a relatively rare inorganic-organic hybrid polyoxo tungstate constructed from sandwich Ni-substituted polyoxo-anions and nickel complexes.     

Synthesis, structure and spectroscopic properties oforganophosphoryl polyoxotungstates of Formula α-[R_2PW_9O_(34)]~(5-)(R=C_6H_5P(S), C_6H_(11)P(O))

Interestandactivityinthechemistryofpolyoxometalatesislargelydrivenbypotentialapplicationincatalysisandmedicine'.Ithasbeenrecorgnizedforalongtimethattheappropriateorganicgroupsonthesurfaceofpolyoxometalatescouldmodifythesolubilityandotherphysicalpropertiesofthecomplexesthatwouldincreasetheirutilityandversatilityincatalysis'-'.Thereactivityoflacunarypolyoxotungstateswithorganicandorganometallicgroupshavebeensummarized'.Tothebestofourknowledge,thereactionoflacunarypolyoxotUngstateswithorgapophosp…     

Synthesis and Crystal Structure of an Organic-inorganic Complex [Hg(DMSO)_2(H_2O)]_2 [GeW_(12)O_(40)]·DMSO·H_2O

Hybrid organic-inorganic compounds have attracted increasing interest in recent years due to the possibility of combination of different characteristics of the compounds to get unusual structures, properties, or applications1. Polyoxometalates (POMs) whic…     

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

A new polyoxomolybdate complex HNa7[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) , β = 125.673(2)°, V = 15210(4) 3, Z = 4, Dc = 2.857 g/cm3, F(000) = 12464, μ = 3.013 mm-1, R = 0.0633 and wR = 0.1654 (I > 2σ(I)). With the bridging sodium cations, the [Mo36O112(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.     

Synthesis and Structural Characterization of [Cu(DMF)_6][(η~5-C_5Me_5)WS_3(CuBr)_3]_2·Et_2O

1 INTRODUCTION In the last decade, we have been interested in the synthesis of [PPh4][(h5-C5Me5)MS3] (M = Mo, W)[1, 2] , Whose organometallic trisulfido anions show high reactivity towards various transition metals[3~6] . We once reported that the reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CH3CN afforded a double incomplete-cubane cluster [PPh4]2[(h5-C5Me5)WS3(CuBr)3]2[3], while the analogous reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CHCl3 gave rise to a 揻our-…     

Synthesis and Crystal Structure of 18-Tungstotetranickel(II) diphosphate Na_(10){(PW_9O_(34))_2Ni_4(H_2O)_2}·26H_2O

1 INTRODUCTIONThe inorganic chemistry concentrating on polyoxometallates, is in a position to connect elementary building blocks and their derivatives in different ways, enabling people to synthesize a large variety of remarkable substances, especially those in the "nanoworld". Of particular importance is the anionic-type which has {MOx}-type building-block units, where M stands for the d block elements in high oxidation states.[1] In 1973 Weakley, Evans and Showell isolated[2] K10P2W1…     

Organophosphoryl polyoxotungstates α-[R2PW9O34]5− [R = PhP(S), C6H11P(O), H2NCH(n-Pr)P(O)]

Tetrabutylammonium salts of organophosphoryl derivatives of tungstophosphate of formula α-[R₂PW₉O₃₄]⁵⁻ [R = PhP(S), C₆H₁₁P(O), H₂NCH(n-Pr)P(O)] have been prepared, purified and characterized by elemental analysis, i.r., ³¹P- and ¹⁸³W-n.m.r. spectroscopy. These anions consist of an α-[PW₉O₃₄]⁹⁻ framework on to which are grafted two equivalent organophosphoryl groups through P–O–W bridges; these new species still retain the ‘unsaturated’ Keggin structure. The five-line ¹⁸³W spectra indicates that the hybrid anions possess C _s symmetry in acetonitrile. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis and Structural Characterization of {[Mn(phen)_2(OAc)(H_2O)]ClO_4}_2H_2O

1 INTRODUCTION Chemistry of manganese cluster has become an attractive research field because of the involvement of manganese in several biological redox-active sys- tems[1,2], especially in the oxygen-evolving complex (OEC) of photosystem Ⅱ (PSⅡ) in green plants[3]. It was thought that the coordination environment of Mn in OEC contains O and N donors, and the bind- ing of aqua to the Mn site may be important to the oxidation of aqua for the evolution of dioxygen[4, 5]. In recent …     

Cerium(III) Complexes with Lacunary Polyoxotungstates. Synthesis and Structural Characterization of a Novel Heteropolyoxotungstate Based on α-[SbW9O33]9− Units

Several cerium(III) complexes with lacunary polyoxotungstates -B-XW₉O^9– ₃₃ (X=As^III, Sb^III) and W₅O^6– ₁₈, have been synthesized and characterized by single-crystal X-ray analysis, elemental analysis and IR spectroscopy. The X-ray analysis of Na₂₅[Ce(H₂O)₅As₄W₄₀O₁₄₀]63H₂O (1) reveals the framework of the well-known [As₄W₄₀O₁₄₀]^28– anion with a {Ce(H₂O)₅}³⁺ unit in the central site S1. The anion in (NH₄)₁₉[(SbW₉O₃₃)₄{WO₂(H₂O)}₂Ce₃(H₂O)₈(Sb₄O₄)]48H₂O (2) consists of a tetrahedral assembly of four -B-Sb^IIIW₉O^9– ₃₃ units connected by two additional six-coordinate tungsten atoms, three nine-coordinate monocapped square-antiprismatic cerium atoms and a Sb₄O₄ cluster. The Ce^III center in the [Ce(W₅O₁₈)₂]^9– anion in Na₉[Ce(W₅O₁₈)]NaCl30H₂O (3) displays the square-antiprismatic environment observed in all complexes of the type [Ln(W₅O₁₈)₂] ^n–.     

A Novel 3D Extended Network Cobalt Paradodecatungstate:Synthesis,Characterization and Crystal Structure of [Co(H_2O)_5]_2[Co(H_2O)_4]_3[H_2W_(12)O_(42)]·11H_2O

1 INTRODUCTION Polyoxometalates are the unique metal-oxygen clusters composed of transition metals in groups V and VI (Mo, W, V, Nb, Ta) in a high oxidation state showing a large structural varieties as well as inte- resting physical and chemical properties in diverse fields including catalysis, analytical chemistry, nanotechnology, chemical sensing, biochemical and geochemical processes, medicine and materials science[1～5]. Recently, there has been increasing interest in the synthesis…     

Synthesis and Crystal Structure of [Zn(FcCOO)_2(2,2'-bipy)(H_2O)]_2·H_2O

A novel complex [Zn(FcCOO)2(2,2'-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) A, α = 90, β = 97.7420(10), γ = 90o, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) A3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I > 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

Synthesis and Crystal Structure of Complex [Pb(qina)_2(DMSO)]·H_2O

A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized,of which qina-is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis,IR spectra,and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system,space group P121/n1,with a=7.1553(17),b=17.543(2),c=17.306(2) ,β=91.671(4)°,C22H20N2O6PbS,Mr=647.65,Z=4,V=2171.5(6) 3,Dc=1.981 g/cm3,μ=7.908 mm-1,F(000)=1248,–9≤h≤6,–23≤k≤19,–22≤l≤22,R=0.0221 and wR= 0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ) . There are also weak interactions,such as π-π interaction,hydrogen bonds and so on,among the complex molecules.     

Crystal Structure and Characterization of Bis(4-isoniazidylthioformyl) Disulfide Hydration Sodium Coordination Polymer:n[(4-Pyridyl-CONHNCS_2)_2~(2-)]·[Na_2(H_2O)_8~(2 )]_n

1 INTRODUCTION Sodium dithiocarbamate is an important industrial reagent, which has been used in many fields[1, 2], such as transition metal extractant[3, 4], floating che- micals of noble metals and efficient toxicide of cadmium poisoning[5]. At present, sodium dithio- carbamates are mainly prepared by the reaction of carbon disulphide with nucleophilic reagents con- taining secondary amine[6, 7]. In the reaction of carbon disulphide with isoniazide, we failed to ob- tain the object compo…     

Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

Synthesis,Characterization and Standard Molar Formation Enthalpy of [Sm(C_7H_5O_3)_2(C_4H_6NO_2S)]·2H_2O

[Sm(C7H5O3)2(C4H6NO2S)]·2H2O was synthesized from the reaction of samarium chloride hexahydrate with salicylic acid and thioproline,and characterized by IR,elemental analysis and thermogravimatric analysis.The standard molar enthalpies of the solutions of SmCl3·6H2O(s),2[C7H6O3(s)],[C4H7NO2S(s)] and [Sm(C7H5O3)2·(C4H6NO2S)·2H2O(s)] in a mixed solvent of absolute ethyl alcohol,dimethyl formamide(DMF) and 3 mol/L HCl were,respectively,determined by calorimetry to be Δs Θ [SmCl3·6H2O(s),298.15 K]=(-46.68±0.15)...     

Hydrothermal Synthesis and Crystal Structure of a Bivanadyl Capped Keggin Polyoxomet alate[Zn(2,2''''-bpy)_2(H_2O)]_2[HPMo_(12)O_(40)(VO)_2]

1 INTRODUCTION The design and synthesis of organic-inorganic hy-brid compounds are of great interest owing to theirextensive theoretical and practical applications in ca-talysis, medicine, analytical chemistry, nanotechno-logy, electrochromism, magnetism and photochemis-try[1～5]. In heteropolyoxometalate chemistry, a newadvance is the decoration of polyoxoanions with va-rious organic and transition metal complex moieties.In contrast to a large number of known organic andtransition-metal-s…     

Hydrothermal Synthesis,Structural Investigation and Characterization of an Organic-inorganic Hybrid, [Co(BⅡM)_3]_2H[BW_(12)O_(40)]·7H_2O

An organic-inorganic hybrid based on α-Keggin-typed [BW12O40]5- anionic cluster, [Co(BⅡM)3]2H[BW12O40]·7H2O(BⅡM = 2,2′-biimidazole), was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490(10), b = 33.270(3), c = 18.9660(16) β = 105.9950(10)°, V = 7490.5(11) 3, C36H50BCo2N24O47W12, Mr = 3905.80, Dc = 3.451g/cm3, μ(MoKα) = 18.886 mm-1, F(000) = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections(I 2σ(I)). The compound consists of two isolated [Co(BⅡM)3]2+ cations and one [BW12O40]5- anion, in which each Co2+ ion is coordinated by six N atoms from three BⅡM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N–H···O(polyoxometalate and water) hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W–Oterminal···πimidazole ring interactions which cooperate with the classical N–H···O hydrogen bonds to stabilize the structural packing.     

Hydrothermal Synthesis and Structural Characterization of the Cage-based Arsenic-Vanadium Microporous Material: [As_2V~(IV)_8V~V_2O_(26)]·8H_2O

Interest in polyoxometalates is expanding rapidly due to the enormous variety of structure topologies leading to interesting and unexpected properties in such diverse field as catalysis, materials science and medicine1-4. Frameworks constructed from square pyramidal, octahedral, tetrahedral units are well documented in the solid-state phases of the V/O/P system5. For the heteropolyanions class of clusters, the V/O/As system has been extensively studied, but the linking of arsenic-vanadium …