[Co（bim）x]配合物修饰的｛P2Mo5O23｝超分子的合成、晶体结构和电化学性质

利用水热技术合成了一种新型[Co(bim)x]配合物修饰的磷钼多金属氧酸盐超分子化合物[Co(bim)3] [Co(Hbim)2( H2 O) P2 Mo5 O23]·5H2O.通过元素分析、红外光谱、热重分析和X射线单晶衍射对化合物进行了表征.化合物属于单斜晶系,P2(1)空间群;晶胞参数:a=11.505 (2) nm,b=19.123 (3) nm,c=13.852(2) nm,α=90.00°,β=100.073(2)°,γ=90.00°,V=3 000.6(8)nm3,F(000)=1 756.0,Z=2.并测试了合成化合物的电化学性质.     

A novel compound with an interpenetrating 2D network structure constructed by [Mo5P2O23] and Ni-4,4'-bipyridine components: its synthesis,characterization and magnetic behaviour

A Novel compound (Hbpy)2[[(H2O)3Ni(bpy)0.5Ni(bpy)(H2O)4]2[Mo5P2O23] [Ni((bpy)0.5)2(H2O)2][Mo5P2O23]].8H2O 1 (bpy = 4,4'-bipyridine) with an interpenetrating 2D network structure was synthesized hydrothermally and characterized by elemental analyses, IR, X-ray single crystal structure analysis and temperature-dependent magnetic susceptibility.     

含氧桥的笼状化合物[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)-[H_3O]~+·1/2(CH_3)_2NCHo·1/2H_2O的合成和结构

[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O(DMF=(CH_3)_2NC-HO)(M_r=1204.67)的晶体属三斜晶系,空间群P,晶胞参数a=16.438(6);b=22.22(1);c=11.325(5),α=104.25(4);β=108.97(3);γ=97.68(4)°,V=3688(3),Z=4,D_c=2.17gcm~(-1),R=0.056,R_w=0.074,晶胞中每个不对称单元含有两个[Mo_5P_2O_(23)]~(6-)[(CH_3)_2NH_2]_5~(5+)[H_3O]~+·1/2DMF·1/2H_2O,阴离子[Mo_5P_2O_(23)]~(6-)中的Mo、P原子成一个畸变五角双锥构型。有一个阴离子的所有原子(Mo、P、O)位置完全确定,而另一个阴离子有一个磷酸根的三个氧原子位置出现二重位置统计分布。化合物的阳离子为二甲胺阳离子和水合氢离子。     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

A building block approach to the synthesis of organic-inorganic oxide materials: the hydrothermal synthesis and network structure of [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (tpypyz = tetra-2-pyridylpyrazine)

The hydrothermal reaction of MoO3, [Ni(CH3CO2)2] x 4H2O, tpypyz, ethylenediphosphonic acid and water yields the 2D material [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (1 x 23H2O), constructed from [Mo5O15(O3PCH2CH2PO3)]4- clusters linked in one-dimension through the ethylene tethers of the diphosphonate component; these molybdodiphosphonate chains are in turn linked into a 2D network through the tetranuclear secondary metal-ligand subunit [Ni4(tpypyz)3]8+.     

Characterization of a new hexasodium diphosphopentamolybdate hydrate, Na6[P2Mo5O23]x7H2O, by 23Na MQMAS NMR spectroscopy and X-ray powder diffraction

A novel hexasodium disphosphopentamolybdate hydrate, Na6[P2Mo5O23]x7H2O, has been identified using X-ray powder diffraction, 1H, 23Na, and 31P magic-angle spinning (MAS) NMR, and 23Na multiple-quantum (MQ) MAS NMR. Powder XRD reveals that the hydrate belongs to the triclinic spacegroup P1 with cell dimensions a = 10.090(3) A, b = 15.448(5) A, c = 8.460(4) A, alpha = 101.45(6) degrees, beta = 104.09(2) degrees, gamma = 90.71(5) degrees, and Z = 2. The number of water molecules of crystallization has been determined on the basis of a quantitative evaluation of the 1H MAS NMR spectrum, the crystallographic unit cell volume, and a hydrogen content analysis. The 23Na MQMAS NMR spectra of Na6[P2Mo5O23]x7H2O, obtained at three different magnetic fields, clearly resolve resonances from six different sodium sites and allow a determination of the second-order quadrupolar effect parameters and isotropic chemical shifts for the individual resonances. These data are used to determine the quadrupole coupling parameters (CQ and eta Q) from simulations of the complex line shapes of the central transitions, observed in 23Na MAS NMR spectra at the three magnetic fields. This analysis illustrates the advantages of combining MQMAS and MAS NMR at moderate and high magnetic fields for a precise determination of quadrupole coupling parameters and isotropic chemical shifts for multiple sodium sites in inorganic systems. 31P MAS NMR demonstrates the presence of two distinct P sites in the asymmetric unit of Na6[P2Mo5O23].7H2O while the 31P chemical shielding anisotropy parameters, determined for this hydrate and for Na6[P2Mo5O23]x13H2O, show that these two hydrates can easily be distinguished using 31P MAS NMR.     

Influence of pH and organic ligands on the supramolecular network based on molybdenum phosphate/strontium chemistry

Three supramolecular materials based on different poly(oxomolybdophosphate) clusters, (H(2)imi)(6)(Himi)(4)[{Sr(H(2)O)(4)}(2){Sr ? P(6)Mo(4)(V)Mo(14)(VI)O(73)}(2)]·17H(2)O (1), (H(2)(4,4'-bpy))(2)[Cu(2)Sr(2)Mo(12)O(24)·(OH)(6)(H(2)O)(6)(H(2)PO(4))(2)(HPO(4))(2)(PO(4))(4)]·5H(2)O (2), and (H(2)bim)(H(2)bim)[SrP(2)Mo(5)O(23)(H(2)O)(3)]·2H(2)O (3) (imi = imidazole, 4,4'-bpy = 4,4'-bipyridine, and bim = 2,2'-biimidazole), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV-vis, XPS and the single-crystal X-ray diffraction. Compound 1 is made up of unusual basket-shape [Sr ? P(6)Mo(18)O(73)](10-) cages linked by [Sr(H(2)O)(4)](2+) fragments to yield unprecedented dimeric chains, which represent the first 1-D assemblies of basket-type POMs. Compound 2 exhibits a novel string constructed from sandwich-like [Cu(P(4)Mo(6)O(31))(2)] units and {Sr(2)Cu} trinuclear linkers. Compound 3 is the first chain of Strandberg-type polyoxoanions connected by Sr(2+) cations. All the 1-D chains are further packed into various 3-D supramolecular assemblies via strong hydrogen-bonding interactions. The electrochemical and electrocatalysis behavior of 1, 2, and 3-CPE have been investigated in detail.     

H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)]的抑酶活性研究

合成了2种过渡金属取代的多酸H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)],并对其抑酶活性进行了研究.结果表明,这2种化合物对酪氨酸酶均有有效的抑制效果.抑制机理表明2种化合物均是可逆竞争型抑制剂.H_8[P_2Mo_(17)Co(OH_2)O_(61)]和H_8[P_2Mo_(17)Ni(OH_2)O_(61)]的半抑制率IC_(50)值分别为(0.434 0±0.000 4)和(0.466 5±0.012 0)mmol/L,抑制常数K_Ⅰ分别为0.216 7和0.220 4mmol/L.该研究能够扩大多金属氧酸盐的应用范围.     

A New Bis-(As_3O_6) Capping 6-Molybdonickelate Complex:Preparation and Characterization of [Ni(en)_2(H_2O)]_2[(NiO_6)Mo_6O_(18)(As_3O_3)_2]·2H_2O

A new complex constructed from a unit with two As3O6 rings capping Anderson-type moieties,[Ni(en)2(H2O)2]2[(NiO6)Mo6O18(As3O3)2]·2H2O(1,en = ethylenediamine),has been hydrothermally synthesized and characterized by IR,single-crystal X-ray diffraction and thermogra-vimetric analysis.The compound crystallizes in triclinic,space group P1 with a = 9.1230(16),b = 11.8078(9),c = 12.2111(9) ,α = 114.5210(10),β = 98.0350(10),γ = 100.0320(10)o,Mr = 2029.80,C8H44As6Mo6N8Ni3O36,V = 1145.0(2) 3,Dc = 2.944 g/cm3,Z = 1,GOF = 0.997,μ = 7.203 mm-1,F(000) = 970,R = 0.0352 and wR = 0.1019.Compound 1 consists of an Anderson-type capped by a two-ring(As3O6) unit [(NiO6)Mo6O18(As3O3)2]4-,two six-coordinate [Ni(en)2(H2O)2]2+ cations and two water molecules.     

Synthesis and Structure Investigation of a Transition Metal Ion Bridging Bis(diphosphopentamolybdates),[H_2BIIM]_3[HBIIM]_4[Mn(H_2O)_4(P_2Mo_5O_(23))_2]·7H_2O

A novel transition metal ion bridging bis(diphosphopentamolybdates) has been synthesized and characterized by elemental analysis,IR spectrum,UV spectrum and single-crystal X-ray diffraction.The single-crystal structure analysis shows that the compound consists of seven charge-compensating 2,2'-biimidazole cations (BIIM=2,2'-biimidazole) and one dumbbell-like [Mn(H2O)4(P2Mo5O23)2]10-heteropolyanion which is constructed by two [P2Mo5O23]6-clusters bridged through one [Mn(H2O)4]2+ cation.     

以[β-Mo_8O_(26)]~(4-)阴离子为构筑块的有机-无机复合物的合成、结构及性质

以[(C4H9)4N]4Mo8O26·nH2O和[Cr3O(C6H5COO)6(H2O)3]NO3为原料,利用常规水溶液法合成了一种由同多阴离子[β-Mo8O26]4-和大阳离子[Cr3O(C6H5COO)6(H2O)3]+通过静电作用形成的有机-无机复合物[Cr3O(C6H5COO)6(H2O)3]4[Mo8O26]·11.5H2O(1).X射线单晶衍射结果表明,该晶体属三斜晶系,P-1空间群,晶胞参数:a=1.545 2(2)nm,b=2.035 1(3)nm,c=2.218 5(3)nm,α=63.097(3)°,β=72.545(3)°,γ=85.114(3)°.对化合物1的热稳定性进行了研究.热重分析表明化合物的失重分两步进行:第一步对应于11.5个结晶水和12个配位水的失去;第二步对应于24个C6H5COO-的失去.     

有机-无机杂化四核镍取代的夹心型砷钨酸盐的合成与晶体结构

在水热条件下,合成了-种有机-无机杂化四核镍取代的夹心型砷钨酸盐[Ni(detaH)2(H2O)]2[Ni(deta)2][Ni4(H2O)2(B-α-AsW9O34)2]·4H2O(deta=二乙烯三胺),并借助IR光谱和X射线单晶衍射对其结构进行了表征.标题化合物属于正交晶系,Pbca空间群,晶胞参数:a=2.16...     

Assembly of three supramolecular compounds based on [P2Mo5O23]6− and Ni(II) complexes

Three supramolecular compounds based on [P₂Mo₅O₂₃]^6? and Ni(II)–bim, [Ni(bim)₃]₃[P₂Mo₅O₂₃]·2H₂O (1), [Ni(Hbim)(bim)₂]₄[P₂Mo₅O₂₃]₂·3H₂O (2), and [Ni(bim)(Hbim)(phen)]₂[P₂Mo₅O₂₃]·7H₂O (3) (bim?=?2,2′-biimidazole, phen?=?1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analysis, single-crystal X-ray diffraction, IR, and TG. All the compounds show 3-D supramolecular networks constructed from weak interactions among free Ni(II) complex, water, and oxygens of [P₂Mo₅O₂₃]^6?. Compound 3 represents the first supramolecular example integrating {Ni(bim)(Hbim)(phen)} with Strandberg-type phosphomolybdate. The compounds display good electrocatalytic activity to reduce hydrogen peroxide and intense fluorescence properties in solution at room temperature.     

一种一维超分子链状四核镍夹心砷钨酸盐的合成和表征(英文)

利用水热方法合成了一种一维超分子链状四核镍夹心的砷钨酸盐[enH2][Ni(en)2]4[Ni4(H2O)2(α-AsW9O34)2].10H2O(1)(en=ethylene diamine);借助元素分析、红外光谱和单晶X射线衍射对其进行了表征。结果表明,化合物1的分子结构单元由1个二支撑的四核镍夹心砷钨酸盐多阴离子{[Ni(en)2]2[Ni4(H2O)2(α-AsW9O34)2]}6-,2个游离的[Ni(en)2]2+配离子,1个游离的双质子化[enH2]2+阳离子和10个结晶水分子组成。有趣的是,相邻的四核镍夹心砷钨酸盐多阴离子{[Ni(en)2]2[Ni4(H2O)2(α-AsW9O34)2]}6-借助Ni…O弱相互作用构筑一维超分子链状结构[Ni…O距离分布在0.253 2～0.283 7nm之间]。     

Bringing an important macrocycle into a polyoxometalate matrix: synthesis, crystal structure, spectroscopy and electrochemistry of [Co(III)(transdiene)(Cl)2]2[Mo6O19], [Ni(II)(transdiene)][W6O19]·DMSO·DCM and [Zn(II)(transdsiene)(Cl)]2[W6O19

Three polyoxometalate based ion pair solids (1-3), in which Co(III) (d(6)), Ni(II) (d(8)) and Zn(II) (d(10)) complexes of a tetra-aza macrocycle, Me(6)-trans-[14]-diene act as the cationic moieties, have been reported. The title complexes, formulated as [Co (C(16)H(32)N(4))(Cl)(2)](2)[Mo(6)O(19)] (1), [Ni(C(16)H(32)N(4))][W(6)O(19)]·DMSO·DCM (2) and [Zn(C(16)H(32)N(4))(Cl)](2)[W(6)O(19)] (3) (C(16)H(32)N(4) = Me(6)-trans-[14]-diene), are the first crystallographic paradigms where transition metal complexes of a Schiff condensed tetra-aza macrocycle have been associated with an isopolyanion, [M(6)O(19)](2-) (M = Mo(vi) and W(vi)). Compounds 1-3 have been characterized through routine spectroscopic analyses including elemental analysis and their structures have been unambiguously determined through single crystal X-ray crystallography. The molecules of compound 1 assemble obeying P1 (#2) space symmetry, whereas those of compounds 2 and 3 follow the higher symmetrical ensemble P2(1)/c (#14). The ESR spectral studies of compounds 1-3 have revealed their diamagnetic (low-spin) nature. The last part of this article describes the electrochemical properties of the title compounds.     

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates:[Cu~Ⅱ_2(HL)_3]_2[Mo_8O_(26)]·(H_2O)_4 and [Ni~Ⅱ(HL)_3]_2(Mo_8O_(26))·(H_2O)_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)).     

Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound:(4,4''-Hbpy)3[NaMo8O26] (4,4''-bpy)2(H2O)4 (bpy = Bipydine)

A novel compound, (4,4'-Hbpy)3[NaMo8O26](4,4'-bpy)2(H2O)4 1 (bpy = bipydine),was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system, space group C2/m with a = 19.1921(5), b = 18.6931(6), c = 9.3821 (3) (A), β = 104.8020(11)°, V = 3254.22(17) (A)3, C50H51Mo8N10NaO30, Mr = 2062.52, Z = 2,F(000) = 2016,μ = 1.591 mm- 1 and Dc = 2.105 g/cm3. The final R = 0.0283 and wR = 0.0912 for 3118 observed reflections (I ＞ 2σ(Ⅰ)). Compound 1 contains the β-[Mo8O26]4- anion, sodium ion, 4,4'-bpy and lattice crystalline water molecules. The β-[Mo8O26] units link the sodium ion to form a chain structure. The infinitechains of [Na(Mo8O26)]3- blocks are surrounded by protonized 4,4'-bpy cations,4,4'-bpy and lattice crystalline water molecules. The 2D-IR correlation spectroscopy study indicates that the stretching vibrations of Mo=O occur more preferentially due to the thermal effect. The TGA analysis shows that compound 1 has high thermal stability.     

Novel charge transfer supramolecular assemblies with Keggin anions and 2-amino-5-nitropyridine

Several novel compounds with the non-linear optical chromophore 2-amino-5-nitropyridine (2A5NP) and Keggin polyoxoanions (alpha-isomers), having the general formula (2A5NP)(m)H(n)[XM12O40].xH2O, M = Mo, W, were synthesised. Compounds were obtained with X = P, n = 3, m = 3 and 4 and X = Si, n = m = 4 (x = 2-6). Thus, for each of the anions [PMo12O40]3- and [PW12O40]3- two different compounds were obtained, with the same anion and organic counterpart but with a different stoichiometric ratio. These presented different charge transfer properties and thermal stability. All compounds were characterised by spectroscopic and analytical techniques. The single crystal X-ray diffraction structure of (2A5NP)4H3[PMo12O40].2.5H2O.0.5C2H5OH showed that the water solvent molecules and the organic chromophores are assembled via infinite one-dimensional chains of hydrogen bonds with formation of open channels, which accommodate [PMo12O40]3- and ethanol solvent molecules.     

Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound: (4,4’-Hbpy)_3[NaMo_8O_(26)](4,4’- bpy)_2(H_2O)_4 (bpy = Bipydine)

1 INTRODUCTION Owing to their unusual topological properties and economically important applications in many fields, such as catalysis, biology, materials science and mag- netochemistry[1～3], polyoxometalates (POMs) have aroused particular interest for a long time[4～6]. But the investigation in their capability and application are relatively less carried on. Even though some POMs have been put into practice, the mechanism of the function of POMs remains incompletely understood. Thus,…     

About the Keggin isomers: crystal structure of [N(C4H9)4]-gamma-[SiMo2W10O40]n- (n= 4 or 6)

The tetrabutylammonium gamma-dodecatungstosilicate has been crystallized in a 6/1 acetonitrile/water solvent. An X-ray single-crystal analysis was carried out on [N(C4H9)4]4-gamma-[SiW12O40] which crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with a = 19.0881(3) A, b = 21.4435(3) A, c = 26.0799(1) A, V = 10674.9(2) A3, Z = 4, and rho(calcd) = 2.392 g/cm3. The idealized C2v arrangement of the anion results from the rotation of 60 degrees of two trigonal [W3O13] groups in the Keggin anion. Taking as reference the geometrical characteristics of the Keggin anion, it appears that the bond lengths and bonds angles within the four [W3O13] groups are not significantly modified while the mu-oxo junctions between the two rotated groups and those between the two unrotated groups involve more acute and opened W-O-W angles, respectively. The syntheses and 183W NMR characterizations of the mixed gamma-[SiW10Mo2O40]n- compounds corresponding to the oxidized (Mo(VI); n = 4) and to the two electron-reduced (Mo(V); n = 6) anions are reported. Structural analysis by 183W NMR has proved unambiguously that the C2v structure of the gamma-[SiW10O36]8- subunit is retained in both the compounds. The electronic behavior of the series gamma-[SiW10M2E2O36]6- (M = Mo or W; E = O or S) is examined, compared and related to 183W NMR data.