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1.
{Na(OCH3)[H3N(CH2)2NH2]2}[WO2(C10H6O2)2] (1) was obtained by the reaction of Na2WO4 · 2H2O with 2,3-dihydroxynaphthalene and ethylenediamine. [H2N(CH2)3NH3]2[WO2(C10H6O2)2] (2) was synthesized by the reaction of Na2WO4 · 2H2O with 2,3-dihydroxynaphthalene and 1,3-propylenediamine. Complex 1 was a one-dimensional chain-like structure and the Na atom is in the structure, while complex 2 was a discrete monomer without Na in its structure. The two complexes were synthesized in the same reaction conditions, except that protonated ethylenediamine was used in reaction 1, but 1,3-propylenediamine in reaction 2.  相似文献   

2.
Three supramolecular complexes, [VO(phen)(C2O4)(H2O)]·CH3OH (1) [(VO)2(u2-C2O4)(C2O4)2(H2O)2]·L·H2O (2), and [(4,4′-bipyH2)0.5]+[VO2(2,6-dipic)]?·2H2O (3) (phen?=?1,10-phenanthroline 4,4′-bipy?=?4,4′-bipyridine, 2,6-dipic?=?2,6-pyridinedicarboxylic, L?=?1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene), have been prepared and characterized by elemental analysis, IR, and UV–vis spectroscopy and single-crystal diffraction analysis. Structural analysis shows that the three complexes all contain carboxylate and V=O moiety; vanadium of 1 and 2 are six coordinate with distorted octahedral geometry with N2O4 and O6 donor sets, respectively, while 3 is five coordinate with distorted trigonal bipyramidal geometry with a NO4 donor set. The complexes exhibit catalytic bromination activity in the single-pot reaction for the conversion of phenol red to bromophenol blue in H2O–DMF at 30?±?0.5?C with pH 5.8, indicating that they can be considered as functional model vanadium-dependent haloperoxidases. In addition, electrochemical behaviors are also studied.  相似文献   

3.
The complexes (NH4)2[MoO2(C2H2O3)2]·H2O, (NH4)2[MoO2(C8H6O3)2] and (NH4)2[MoO3(C4H4O6)]·H2O were prepared by reaction of MoO3 with glycolic, mandelic and tartaric acids, respectively. The complexes were characterized by elemental and thermal analysis, IR spectroscopy and X-ray diffraction. Crystals of the glycolate and tartarate complexes are orthorhombic and the mandelate complex is monoclinic. Elemental and thermal analysis data showed that the glycolate and tartarate complexes are monohydrated. Hydration water is not present in the structure of the mandelate complex. IR spectra showed COO? is involved in coordination as well as the oxygen atom of the deprotonated hydroxyl group of the α-carbon. The glycolate molybdenum complexes with general formula M2[MoO2(C2H2O3)2nH2O, where M is an alkali metal and n?=?1 or ½, were also prepared and characterized. Aqueous solutions of the glycolate complex become blue and mandelate and tartarate complexes change to yellow or brown when exposed to UV-radiation.  相似文献   

4.
Two three-dimensional supramolecular water architectures, [Zn(phen)3]2·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O (1) and [Co(phen)3]2·[Co(H2O)6]·(C10H16O4)3·30H2O (2) [phen = 1,10-Phenanthroline, C10H16O4 = sebacic dianion], have been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions. The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.  相似文献   

5.
In this study, a series of compounds based on Dawson-type phosphomolybdates, H3(C6NO2H6)2[K(H2O)3(C6NO2H5)3][P2Mo18O62] ? 5.5H2O (1), (C6NO2H6)6[Ln(H2O)7(C6NO2H5)2]2[P2Mo18O62]2·13.5H2O (Ln = Ce (2), La (3)) have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy methods, TG analysis, and single-crystal X-ray diffraction. Compound 1 consists of [P2Mo18O62]6? building units joined by potassium-pyridine-3-carboxylic acid complexes, resulting in a wavelike polyoxometalate (POM) chain, which further interacts with each other via intermolecular interactions to form a 3-D supramolecular channel framework containing guest water molecules. Compounds 2 and 3 possess a 3-D supramolecular framework with 1-D tunnel constructed from [P2Mo18O62]6? and mononuclear lanthanide coordination complex fragments. To the best of our knowledge, 1 not only represents the first example of 1-D hybrid assembly based on Dawson-type phosphomolybdate, but also the first hybrid compound constructed from Dawson-type POMs and alkali–metal coordination complex fragments.  相似文献   

6.
Bis(disulfido)bridged NbIV cluster oxalate complexes [Nb2(S2)2(C2O4)4]4– were prepared by ligand substitution reaction from the aqua ion [Nb2(μ‐S2)2(H2O)8]4+ and isolated as K4[Nb2(S2)2(C2O4)4] · 6 H2O ( 1 ), (NH4)6[Nb2(S2)2(C2O4)4](C2O4) ( 2 ) and Cs4[Nb2(S2)2(C2O4)4] · 4 H2O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.  相似文献   

7.
By selecting appropriate ligands, two polyoxidovanadate complexes, [Ni(en)2]3[V18O42Cl]·7H2O·2H3O+ (1) and [H2N(CH3)2]3[PV14O42]·2TMP·6H3O+ (2), have been synthesized at different pH values using V2(SO4)3, Ni(CH3COO)2, and H6TTHA (for 1), VO(acac)2 and TPP (for 2) (en = C2H8N2, TPP = thiamine pyrophosphate, TMP = thiamine monophosphate, H6TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid). The complexes have been characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TG), and single crystal X-ray diffraction. The complexes catalyze the oxidation of the organic substrate phenol red in the presence of H2O2 and bromide, and the reaction system is considered as a model for hydrogen peroxide determination. The reaction rate constants (k) for 1 and 2 are calculated as 3.729 × 103 and 4.083 × 103 (mol L)?2 s?1. The maximum conversion rate of phenol red for 1 is 83.32%, while for 2 is 81.12%.  相似文献   

8.
In this paper, we have illustrated the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with varieties of guest molecules. A flexible molecule N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors was designed, capable of forming N–H…Cl hydrogen bonds with a crystallographically unique chloride anion, to construct an anion-directed ligand. The pillared double-layered host framework was constructed by an anion-directed ligand and primary coordination sphere [CoCl4]2 ?  through weak C–H…Cl hydrogen-bonding interactions. A variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of novel supramolecular inclusion solids: [L1]·4[H]+·[CoCl4]2 ? ·2Cl·1.5[C8H8O2]·0.25[CH3OH] (1) and [L1]·4[H]+·[CoCl4]2 ? ·2Cl·1.5[C12H20O4]·0.5[CH3OH] (2).

We have presented herein the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with a variety of guest molecules. A novel type of a pillared double-layered host framework was constructed by a second-sphere coordination between the anion-directed ligand (L1 = N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine) and [CoCl4]2 ?  through weak C–H…Cl hydrogen-bonding interaction, and a variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of supramolecular inclusion solids: [L1]·4[H]+·[CoCl4]2 ? ·2Cl·1.5[C8H8O2]·0.25[CH3OH] (1) and [L1]·4[H]+·[CoCl4]2 ? ·2Cl·1.5[C12H20O4]·0.5[CH3OH] (2)

  相似文献   

9.
Asymmetric citrato dioxovanadates(V), [Hneo]4[V2O4(R-Hcit)(OH)][V2O4(S-Hcit)(OH)]?·?4H2O (1) and [Ni(phen)3]2[V2O4(R-Hcit)(OC2H5)][V2O4(S-Hcit)(OC2H5)]?·?4H2O (2) and (H4cit?=?citric acid, neo?=?2,9-dimethyl-1,10-phenanthroline, phen?=?1,10-phenanthroline) are isolated with the help of large counterions. Structural analyses of complexes 1 and 2 show that vanadium atoms are coordinated by tridentate citrate ligand and hydroxy or ethoxy groups, respectively. The insertions of hydroxy and ethoxy groups give new examples of the mixed RO-bridges for vanadium–citrate complexes.  相似文献   

10.
Two complexes, [Cu2(TFSA)(2,2′-bpy)4]?·?TFSA?·?8H2O (1) and {[Cu(4,4′-bpy)(H2O)2]?·?TFSA?·?6H2O} n (2) (H2TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2?} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2?} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O?···?(H2O)6?···?H2O?] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.  相似文献   

11.
Two new inorganic–organic hybrid polyoxotungstates [enH2][C8N4H22]3H2[Co4(enH)2(GeW9O34)2] · 6H2O (1) and [Co(en)3]2H6[Co4(enH)2(GeW9O34)2] · 14H2O (2) (en = ethylenediamine) have been synthesized by hydrothermal methods and characterized by IR, TG, XRD, XPS, elemental analysis, and single-crystal X-ray analysis. The polyoxoanion frameworks of the two compounds consist of two classical tetra-Co sandwiched polyoxoanions [Co4(H2O)2(GeW9O34)2] in which two organic ligands substitute two water molecules. The tetra-Co clusters in 1 and 2 exhibit the familiar structural type of a β-junction at the sites of metal incorporation. Compound 1 is of interest owing to its C8N4H20 ligands resulting from the reaggregation of triethylenetetramine which occurs under 160°C.  相似文献   

12.
Two compounds of disphosphopentamolybdate(VI) with the formulae (C4H14N2O)3- [P2Mo5O23]?·?3H2O (1) and (C4H14N2O)5(NH4)2[P2Mo5O23]2?·?5H2O (2) have been synthesized by a simple, fast and efficient microwave method, and their crystal structures and spectroscopic properties have been studied. The heteropoly anion [P2Mo5O23]6? has a known structure built of five MoO6 octahedra and two PO4 tetrahedra. The MoO6 octahedra form a pentagonal ring by sharing four edges and one corner and the PO4 tetrahedra are attached to one side of the ring by three oxygen atoms. The most interesting feature of compound 1 is its extensive framework based on a one-dimensional zigzag chain. In compound 2, a more extensive and complicated framework of hydrogen bonds joins the anions, organic cations and water molecules together.  相似文献   

13.
The syntheses and crystal structures of the closely related but non-isostructural Cd2(C19H21N3O3F)4(H2O)2?·?4H2O (1) and Pb2(C19H21N3O3F)4?·?4H2O (2) are described, where C19H21N3O3F? is enrofloxacinate (enro). Both compounds contain centrosymmetric, binuclear, neutral complexes incorporating a central diamond-shaped M2O2 (M?=?Cd, Pb) structural unit. The Cd2+ coordination polyhedron in 1 is a CdO6 trigonal prism, including one coordinated water. The Pb2+ coordination polyhedron in 2 can be described as a very distorted square-based PbO5 pyramid, although two additional short Pb?···?O (<3.1?Å) contacts are also present. In the crystal of the cadmium complex, O–H?···?O hydrogen bonds lead to a layered structure. In the lead compound, O–H?···?O and O–H?···?N interactions lead to chains in the crystal. Crystal data: 1: C76H96Cd2F4N12O18, M r?=?1766.45, triclinic, P 1, a?=?12.185(2)?Å, b?=?12.306(3)?Å, c?=?14.826(3)?Å, α?=?68.15(3)°, β?=?70.28(3)°, γ?=?86.11(3)°, V?=?1938.2(7)?Å3, Z?=?1, T?=?298 K, R(F)?=?0.030, wR(F 2)?=?0.079. 2: C76H88F4N12O16Pb2, M r?=?1920.00, triclinic, P 1, a?=?12.0283(4)?Å, b?=?12.7465(4)?Å, c?=?13.0585(4)?Å, α?=?83.751(1)°, β?=?74.635(1)°, γ?=?81.502(1)°, V?=?1904.3(1)?Å3, Z?=?1, T?=?298?K, R(F)?=?0.021, wR(F 2)?=?0.049.  相似文献   

14.
A new general synthetic procedure for preparation of Na3[Fe(C2O4)3]·5H2O (1), Rb3[Fe(C2O4)3]·3H2O (2), and Cs3[Fe(C2O4)3]·2H2O (3) was developed. The crystal structures of these salts have been determined by single crystal X-ray diffraction. Salt 1 crystallizes in the monoclinic space group C2/c with Z = 8, salt 2 in P21/c with Z = 4, and salt 3 in P21/n with Z = 4. The three new salts and K3[Fe(C2O4)3]·3H2O, prepared for comparative purposes, were further characterized by infrared and 57Fe-Mössbauer spectroscopy. These spectra are discussed in comparison with those of related oxalato complexes.  相似文献   

15.
Two new inorganic–organic hybrid cobalt phosphomolybdates (Hdien)2[Co(dien)]2[Co(dien)(H2O)]2[CoMo12O24(HPO4)2(H2PO4)2(PO4)4(OH)6]?···?5H2O (1) and (H2dien)2[Co(dien)]2[Co(H2O)2]2[CoMo12O24(HPO4)4(PO4)4(OH)6]?···?7H2O (2) (dien?=?diethylenetriamine), involving molybdenum in the V oxidation state and covalently bonded transition metal complexes, have been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 exhibits a one-dimensional (1D) chain framework, in which dien molecules adopt two kinds of coordination modes. Compound 2 shows a two-dimensional (2D) layer framework with three types of unusual tunnels. To the best of our knowledge, it is the first time [Co(dien)] units are directly incorporated into 1D and 2D skeletons of reduced molybdenum phosphates. The electrochemical properties of the two compounds were studied via the method of bulk-modified carbon paste electrodes. Furthermore, the magnetic properties of compound 2 are reported.  相似文献   

16.
Preparation of the Free 12-Tungstoaluminium Acid H5[AlO4W12O36] · 6 H2O by Means of the Cryogenic Method The title compound was first prepared in solid state from its aqueous solution by means of the cryogenic method and characterized by chemical and thermal analyses, IR and UV spectroscopy. From X-ray heating patterns the formation of a new cubic phase 1/2 Al2O3 · 12 WO3 (I) at 400°C was found, being stable till 830°C: a = 378 pm (600°C). High-resolution 27Al NMR (MAS-technique) was used to determine the tetrahedral coordination of aluminium in the title compound and the octahedral coordination in I. The degradation of the doped WO3-phase I into Al2(WO4)3 begins at 600°C. Above 830°C tetragonal WO3 and Al2(WO4)3 coexist.  相似文献   

17.
Two new linear trinuclear complexes, [Co(NiL1)2(SCN)2] (1) and [Co(NiL2)2(H2O)2](ClO4)2?·?2C2H5OH (2), have been prepared by using Co(ClO4)2?·?6H2O and two macrocyclic complex ligands NiL1 and NiL2. L1 and L2 are the doubly deprotonated forms of dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazabicyclo[12.4.015,16]13,18-dicarboxylate and dimethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate, respectively. X-ray single crystal analyses reveal the coordination geometries around Ni(II) in both 1 and 2 are identical and slightly distorted square planar with N4 donors; all Ni–N bonds in the two complexes are very short. The Co(II) ions are at the centers of the trinuclear complexes and have distorted octahedral coordination geometries of O4N2 donors in 1 and an O6 in 2. π?···?π interactions involving aromatic and non-aromatic π-systems join the trinuclear entities to form 2-D layers in the crystals of 1 and 2.  相似文献   

18.
Two polyoxometalate-based inorganic metal-organic hybrid supramolecular complexes [Cu(2,2′-bpy)2]2[VIV 2MoV 5MoVI 7O38(PO4)] (1) (2,2′-bpy?=?2,2′-bipyridine) and [Cu(2,2′-bpy)2]2[MoVMoVI 11O36(PO4)]?·?3H2O (2), have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. Both complexes are constructed from polyoxoanions (the bivanadyl capped α-Keggin polymolybdate anion [VIV 2MoV 5MoVI 7O38(PO4)]4? for 1 and the reduced 12-molybdophosphate anion [MoVMoVI 11O36(PO4)]4? for 2) and copper(II) complex cations [Cu(2,2′-bpy)2]2+, forming two-dimensional (2D) layer network structures, in which the polyoxoanion and the complex fragment cation connect with each other through Cu?···?Opolyoxoanion short contact weak interactions, which mediate ferromagnetic interaction.  相似文献   

19.
Four new network organic–inorganic hybrid supramolecular compounds [PW12O40](C2H4N3)3·6H2O (1), [PMo12O40](C2H4N3)3·6H2O (2), [H4SiW12O40]8[C6NO2H4]4[C6NO2H5]16[C5NH6]4·39H2O (3) and [H3VW12O40] (C6H6NO2)2(CHO2)2·4H2O (4) composed by keggin type heteropolyanion and O/N-containing organic groups of 1H-1,2,4-Triazole or 2,3-Pyridinedicarboxylic acid have been successfully synthesized by hydrothermally method, and characterized by infrared spectrum (IR), thermogravimetric–differentialthermal analysis (TG–DTA), cyclic voltammetry (CV) and single crystal X-ray diffraction (XRD). Compounds 1–4 exhibit three dimensional supramolecular network via hydrogen bonds and/or π–π stacking interactions. These compounds exhibit good thermal stability and catalytic ability. They are active for catalytic oxidation of methanol in a continuous-flow fixed-bed micro-reactor, when the initial concentration of methanol is 2.5 g m?3 in air and flow rate is 10 mL min?1, the corresponding elimination rates of methanol are 65% (125 °C), 85% (125 °C), 94% (150 °C), and 80% (125 °C), respectively.  相似文献   

20.
The thermal behaviour of four coordination compounds (NH4)6[Y3Fe5(C4O5H4)6(C4O5H3)6]·12H2O, (NH4)6[Y3Fe5(C6O7H10)6(C6O7H9)6]·8H2O, (NH4)6[Er3Fe5(C4O5H4)6(C4O5H3)6]·10H2O and (NH4)6[Er3Fe5(C4O6H4)6(C4O6H3)6]·22H2O has been studied to evaluate their suitability for garnet synthesis. The thermal decomposition and the phase composition of the resulted decomposition compounds are influenced by the nature of metallic cations (yttrium-iron or erbium-iron) and ligand anions (malate or gluconate).  相似文献   

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