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1.
 Anhydrous 1,6-hexanediammonium dihydrogendecavanadate ((HdaH2)2H2V10O28, 1) was prepared by reaction of V2O5 with 1,6-hexanediamine in aqueous solution. The crystal structure of 1 was determined, and the proton positions in the H2V10O28 4− anion were calculated by the bond length/bond number method. The protons are bound to the centrosymmetrically oriented μ–OV3 groups of the decavanadate anion. Based on the analysis of IR spectra of 1 prepared from H2O and D2O, the absorption band at 871 cm−1 can be attributed to δ(V–Ob–H) vibrations.  相似文献   

2.
Three heteonuclear complexes containing [V10O28]6− units, {[Cu(pyr)(H2O)4]2(H3O)2[V10O28] · 13.5H2O}n (1), {[Ni(pyr)(H2O)4]2(H3O)2[V10O28] · 9.5H2O}n (2) and [Zn2(H2O)14(V10O28)] · H2PPZ (3) are synthesized and characterized by elemental analyses, IR, single crystal X-ray analyses. The complex 1 and 2 have the similar structures which are composed of the [V10O28]6− cluster anion and 1D chain {[M (pyr)(H2O)4]2+}n (M = Cu Ni) cations bridged by pyrazine. In the complex 3, Zn2+ with two coordination modes is bridged by water molecules to build 1D zigzag chains, and then is linked to the bridging oxygen atoms from [V10O28]6− to generate a 2D grid architecture filled with the protoned piperazine (PPZ) molecules. In this paper, the magnetic properties of complex 2 are characterized.  相似文献   

3.
Summary.  Oxo peroxo glycolato complexes of vanadium(V) (M 2[V2O2(O2)2(C2H2O3)2nH2O (n=0, 1; M=NBu4 + (1), K+ (2), NH4 + (3), Cs+ (4), NPr4 + (5)) as well as (NBu4)2[V2O4(C2H2O3)2]ċ H2O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V2O2(O2)2(C2H2O3)2]2− anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array. Received July 12, 1999. Accepted (revised) October 28, 1999  相似文献   

4.
Vanadium(V) oxido peroxido tartrato complexes have been prepared from aqueous-ethanolic media and characterized by spectroscopic methods. Using racemic tartaric acid for the synthesis, the simultaneous crystallization of racemic compounds (racemic phases) and racemic conglomerates (chiral phases) has been observed. The X-ray crystal structure of (NH4)4[V2O2(O2)2((2R,3R)–H2tart)2(μ–H2O)][V2O2(O2)2((2S,3S)–H2tart)2(μ–H2O)]·8H2O (tart = C4H2O6 4−) revealed that the dinuclear anion is composed of two pentagonal bipyramidal polyhedra about vanadium atoms, which are joined to each other by sharing two oxygen atoms of hydroxyl groups and an oxygen atom from a bridging water ligand. The prepared compounds are not stable in aqueous solution; 51V NMR spectra exhibit the signals of several peroxido and non-peroxido vanadium(V) complexes.  相似文献   

5.
Decavanadates with complex cations, (NH4)2[Zn(H2O)5(NH3CH2CH2COO)]2V10O28·4H2O (4) and (NH4)2[Mn(H2O)5(NH3CH2CH2COO)]2V10O28·2H2O (5), have been prepared and characterized by elemental analysis, i.r., Raman, UV–vis. and 51V-n.m.r. spectroscopies and by thermal analysis. The X-ray structure determination revealed, both in 4 and 5, the presence of complex cations with hexacoordinated central atoms and monodentate β-alanine ligands, and decavanadate V10O28 6− anions. The differences in the structural arrangement in 4 and 5 are probably a consequence of the different ionic radii of Zn2+ and Mn2+ (high spin).  相似文献   

6.
Two new decavanadate metal complexes, [Co(H2O)6]2[H2V10O28]·6H2O (1) and (NH4)2[Ca(H2O)7]2[V10O28] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO3 solution with an aqueous solution of CoCl2·6H2O were used for generating 1 and aqueous CaCl2·2H2O and NH4VO3 solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H2O)6]2+ cations, [H2V10O28]4− anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H2O)7]2+ cations, ammonium NH4 + and [V10O28]6− anion. For compound 2, the distorted pentagonal bipyramid [Ca(H2O)7]2+ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.  相似文献   

7.
Two novel organic–inorganic hybrid vanadoantimonate compounds, [Zn2(dien)3][{Zn(dien)}2V16Sb4O42(H2O)]·4H2O (1) and [Zn(dien)2]2 [{Zn(dien)}2(V14Sb8O42)2(H2O)]·4H2O (2) (dien = Diethylenetriamine), have been synthesized hydrothermally at different pH value, and structurally characterized by elemental analyses, FT-IR, XPS, TGA and single crystal X-ray diffraction analysis. Compound 1 is composed of the rare [V16Sb4O42]8− cluster covalently linked by two [Zn(dien)]2+ coordination cations to yield a novel one-dimensional linear chain. Compound 2 exhibits a one-dimensional zigzag chain constructed from the [V14Sb8O42]4− cluster and [Zn(dien)]2+ coordination polymer. The two examples represent the first one-dimensional assemblies based on vanadoantimonate cluster and the metal–organic complex moieties.  相似文献   

8.
Two Keggin-type phosphododecamolybdate compounds [Cd(2,2′-bpy)3]2[PMoVMoVI 11O40] (1) and [H3PMo12O40]·3(4,4′-bpy)·4H2O (2) (bpy=bipyridine) were prepared by the hydrothermal method for the first time and characterized by elemental analyses, X-ray single-crystal diffraction, ESR spectra, and IR spectra, showing that compound 1 consists of a mixed valence Keggin polyanion [PMoVMoVI 11O40]4− and two isolated coordinated cations [Cd(2,2′-bpy)3]2+, while compound 2 is an intermolecular compound based on organic substrate 4,4′-bpy and heteropoly acid unit H3PMo12O40. Furthermore, both the compounds show strong photoluminescence properties in the solid state at room temperature. The catalytic activities of the two compounds were also determined by the oxidation of benzaldehyde to benzoic acid using H2O2 as oxidant in a liquid–solid triphase system.  相似文献   

9.
Four novel organic–inorganic hybrid compounds [Cu5 I(4,4′-bpy)3(2,2′-bpy)4][BW12O40] · H2O (1), [Ni0.5(2,2′-bpy)1.25][Ni(2,2′-bpy)3][Ni(2,2′-bpy)2(H2O)(SiW11VIWVO40)] · 0.5H2O (2), [H2bpy]2[Zn(2,2′-bpy)3]2[Si2W18O62] · 1.5H2O (3) and [CuII(2,2′-bpy)2]2[SiW12O40] · 2H2O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW12O40]5− polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW11VIWVO40]5− polyoxoanions supported by [Ni(2,2′–bpy)2]2+. Compound (3) is composed of a novel [Si2W18O62]8− cluster and [Zn(2,2′–bpy)3]2+ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)2]2+ coordination polymer fragments, resulting in 3D networks via supramolecular interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

10.
Two supramolecular crown ether complexes [Na(DC18C6-A)(H2O)]{[Na(DC18C6-A)][Cd(mnt)2]} (1) and [K(DC18C6-A)]2[Cd(mnt)2] (2) (DC18C6-A = cis-syn-cis-dicyclohexyl-18-crown-6, isomer A; mnt = maleonitriledithiolate) have been synthesized and characterized by elemental analysis, FT-IR spectroscopy and X-ray single crystal diffraction. Complex 1 is composed of one [Na(DC18C6-A)(H2O)]+ complex cation and one {[Na(DC18C6-A)][Cd(mnt)2]}complex anion and displays an infinite chain-like structure through N–Na–N interactions. In complex 2, [K(DC18C6-A)]+ complex cation and [Cd(mnt)2]2− complex anion afford a novel 1D ladder-like structure by N–K–N, N–K–S interactions.  相似文献   

11.
 Oxo peroxo glycolato complexes of vanadium(V) (M 2[V2O2(O2)2(C2H2O3)2nH2O (n=0, 1; M=NBu4 + (1), K+ (2), NH4 + (3), Cs+ (4), NPr4 + (5)) as well as (NBu4)2[V2O4(C2H2O3)2]ċ H2O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V2O2(O2)2(C2H2O3)2]2− anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array.  相似文献   

12.
Two rare earth vanadyl complexes incorporating N-(p-benzoic acid methylene)imino dimethylene phosphonic acid, {[Ce(H2O)7]2[V10O28]}·11H2O (1) and {[Gd(H2O)7]2[V10O28]}·11H2O (2) were synthesized and characterized by IR spectra, UV-Vis spectra, Fluorescence spectra and single crystal X-ray analysis. In complexes 1 and 2, they are isomorphism, triclinic, space group P-1, V5+ ion for the hexa-coordinate with oxygen constitute [V10O28] 6− cluster, in which oxygen were taken μ1, μ2, μ3, μ6 method of allocation. Ce3+ ion is nine-coordinate. Complex 1 has a very strong selective of Zn2+ from the fluorescence spectra, and can as highly selective probes for Zn2+.  相似文献   

13.
New chromium(III) complexes, [Cr(C2O4)2(2-hnic)]2− and [Cr(C2O4)2(3-hpic)]2− (where 2-hnic = O,O′-bonded 2-hydroxynicotinic acid and 3-hpic = N,O-bonded 3-hydroxypicolinic acid), were obtained and characterized in solution. The acid-catalyzed aquation of the both complexes leads to liberation of the appropriate pyridinecarboxylic acid and formation of cis-[Cr(C2O4)2(H2O)2]. Kinetics of these reactions were studied spectrophotometrically in the 0.1–1.0 M HClO4 range, at I = 1.0 M. In the case of [Cr(C2O4)2(2-hnic)]2−, a slow chelate-ring opening at the Cr–O (phenolate) bond is followed by a fast Cr–O (carboxylate) bond breaking. The rate law: kobs = kHQH[H+] was established, where kH is the acid-catalyzed rate constant and QH is the protonation constant of the coordinated phenolate oxygen atom. In the case of [Cr(C2O4)2(3-hpic)]2−, the reversible chelate-ring opening at Cr–N bond is followed by the rate determining step – the one-end bonded ligand liberation. The rate law for the first step was determined: kobs = k1+k−1/Q1[H+], where k1 and k−1 are the rate constants of the chelate-ring opening and closure and Q1 is the protonation constant of the pyridine nitrogen atom. The aquation mechanisms are proposed and the effect of ligand coordination mode on complex reactivity is discussed.  相似文献   

14.
Three new organic–inorganic hybrid complexes based on the Wells–Dawson polyoxoanion, namely (H2bpp)[Ni2(bpp)2(H2O)4(P2W18O62)]·H2O 1, [Cu6(Hbpy)6(bpy)3(P2W18O62)2]·2H2O 2 and (Him)5[Cu(im)2(P2W18O62)]·4H2O 3 [bpp = 1,3-bis (4-pyridyl) propane, bpy = 4,4′-bipyridine, im = imidazole] have been synthesized and characterized. Complex 1 exhibits a three-dimensional (6, 3)-connected framework with anatase topology constructed from [α-P2W18O62]6− clusters and [Ni(bpp)]2+ fragments. Each [α-P2W18O62]6− anion links to six nickel atoms through six terminal oxygen atoms from four polar and two equatorial WO6 octahedra, which shows a novel coordination mode of a Wells–Dawson cluster with a transition-metal atom. Complex 2 displays an interesting one-dimensional double-chain structure built from [α-P2W18O62]6− clusters and [Cu2(bpy)(Hbpy)2]2+ fragments. To our knowledge, complex 2 represents the first double-chain organic–inorganic hybrid complex based on a Wells–Dawson-type cluster. Complex 3 possesses a one-dimensional zigzag chain structure constructed from [α-P2W18O62]6− anions and [Cu(im)2]+ units through weak Cu···O interactions.  相似文献   

15.
The phase and chemical compositions of the precipitates forming in the Sr(VO3)2-VOCl2-H2O system in the V4+/V5+ = 0.11–9 range at 80–90°C are reported. At pH 1–3 and V4+/V5+ = 0.25−9, the general formula of the precipitated compounds is Sr x V y 4+ V12−y 5+O31−δ·nH2)(0.37 ≤ x ≤ 1.0, 1.7 ≤ y ≤ 3.0, 0.95 ≤ δ ≤ 2.1). Polyvanadates containing the largest amount of vanadium(IV) are obtained at an initial V4+/V5+ ratio of 9 and pH 1.9. Precipitation from solutions at pH 3 takes place only in the presence of the VO2+ ion, and the highest precipitation rate is observed at V4+/V5+ = 0.11. The process is controlled by a second-order reaction on the polyvanadate surface. Under hydrothermal conditions at 180°C, Sr0.25V2O5·1.5H2O nanorods are obtained from solutions with a V4+/V5+ molar ratio of 0.1 at pH 3. The nanorods, 30–100 nm in diameter and up to 2–3 μm in length, have a layered structure with an interlayer spacing of 10.53 ± 0.08 ?.  相似文献   

16.
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement. Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the U–O bonds of the uranyl cation. Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users.  相似文献   

17.
 The most stable structures of V x O y +/V x O y (x=1, 2, y=1–5) clusters and their interaction with O2 are determined by density functional calculations, the B3LYP functional with the 6-31G* basis set. The nature of the bonding of these clusters and the interaction with O2 have been studied by topological analysis in the framework of both the atoms-in-molecules theory of Bader and the Becke–Edgecombe electron localization function. Bond critical points are localized by means of the analysis of the electron density gradient field, ∇ρ(r), and the electron localization function gradient field, ∇η(r). The values of the electron density properties, i.e., electron density, ρ(r), Laplacian of the electron density, ∇2ρ(r), and electron localization function, η(r), allow the nature of the bonds to be characterized, and linear correlation is found for the results obtained in both gradient fields. Vanadium-oxygen interactions are characterized as unshared-electron interactions, and linear correlation is observed between the electron density properties and the V–O bond length. In contrast, O2 units involve typical shared-electron interactions, as for the dioxygen molecule. Four different vanadium–oxygen interactions are found and characterized: a molecular O2 interaction, a peroxo O2 2− interaction, a superoxo O2 interaction and a side-on O2 interaction. Received: 15 October 2001 / Accepted: 30 January 2002 / Published online: 24 June 2002  相似文献   

18.
The alkoxido-titanium pentamolybdate [(iPrO)TiMo5O18]3− (1) has been obtained as its tetrabutylammonium (TBA) salt by hydrolysis of a mixture containing (TBA)2[Mo2O7], (TBA)4[Mo8O26] and Ti(OiPr)4 in MeCN and has been characterised by 1H, 13C, 17O, 49Ti and 95Mo NMR and FTIR spectroscopy, electrospray ionisation mass spectrometry, elemental microanalysis and single-crystal X-ray crystallography. The Lindqvist-type structure is derived from [Mo6O19]2− by replacement of {Mo=O}4+ by {(iPrO)Ti}3+ and shows bond alternation in the TiMo3O4 rings, with average bond distances of 1.956(8) ? for Ti–O(Mo), 1.832(7) ? for Mo–O(Ti), 1.943(7) ? for Moeq–O(Moax) and 1.910(6) ? for Moax–O(Moeq), while the increase in charge results in a decrease in 17O NMR chemical shift for terminal Mo=O groups from δ 933 for [Mo6O19]2− to δ 875 and 857 for 1 and a shift in νMo=O from 951 cm−1 for [Mo6O19]2− to 930 cm−1 for 1. The main peaks in the negative-ion electrospray ionisation mass spectrum of (TBA)3 1 could be assigned to ion aggregates containing 1 or fragments derived from 1, including {(TBA)2[(iPrO)TiMo5O18]}, {(TBA)[(iPrO)TiMo5O18]}2−, {(iPrO)TiMo2O8}, {TiMo5O18}2−, {TiMo4O15}2− and {Mo3O10}2−.  相似文献   

19.
A novel polyoxometalate compound consisting of monolacunary Wells-Dawson anions and trivalent lanthanide cations, K4Na2H2[Ce2(H2O)122-P2W17O61)]2·10H2O (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental analyses, IR spectrum, UV spectrum and TG analyses. Single crystal X-ray diffraction reveals that CeIII ions occupy the lacunary site in the ‘cap’ regions of the Wells-Dawson ions and at the same time combine with a terminal oxygen atom of another Wells-Dawson anion, forming a centrosymmetric dimeric cluster [{Ce(H2O)42-P2W17O61)}2]14−. Furthermore, the dimeric clusters act as a bidentate ligand and coordinate two [Ce(H2O)8]3+ fragments with two terminal oxygen atoms. The bisupporting dimers are linked via K-bridge, W9–O9–K1–O13–W13, and Na-bridge, W1–O1–Na1–O15–W15, forming one-dimension (1D) chains and the chains are further connected into 3D architecture also by the potassium ions. Additionally, the electrochemistry activity of compound (1) is reported. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.  相似文献   

20.
Two ammonium decavanadate(V) compounds, (H2tmen)3V10O28·6H2O (1) and (H2en)3V10O28·2H2O (2), where H2tmen and H2en represent the doubly protonated N,N,N′,N′-tetramethylethylenediammonium ion and doubly protonated ethylenediammonium ion, respectively, have been synthesized and structurally characterized by elemental analyses, spectroscopic (i.r., e.s.r.) studies, and single-crystal X-ray diffraction. Both crystal structures reveal the presence of the [V10O28]6− cluster anions, doubly protonated diammonium cations, and lattice water molecules. Hydrogen bonds assemble these two compounds to form three-dimensional networks. The in vitro anticancer activity against A549 and P388 tumor cells lines has also been determined by the MTT-based assay, and the results suggest that both compounds can inhibit proliferation of these two kinds of tumor cells.  相似文献   

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