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1.
Two new organic–inorganic hybrid compounds, [CuII(btb)1.5(γ-Mo8O26)0.5(H2O)]·2H2O (1) and [CuII2(btb)4(PMoVMoVI11O40)]·2H2O (2) (btb = 4-butyl-1,4-bis(1,2,4-triazole), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectra and elemental analyses. In 1, there exists a ladder-like metal-organic chain with the bidentate [γ-Mo8O26]4? anions inserting into the grids. Adjacent chains share the same Cu-btb lines of the ladder to form a 2-D layer. Compound 2 also has a ladder-like metal-organic chain. The tetradentate [PMo12O40]3? anions embed in the grids. The same Cu-btb line is shared by adjacent chains to build a 2-D layer. The btb ligands link adjacent layers to form a 3-D framework. Moreover, we also have investigated the electrochemical and photocatalytic properties of 1 and 2.  相似文献   

2.
Two Keggin-type heteropolyanions were synthesized and characterized by X-ray crystal structure and elemental analysis as well as infrared spectroscopy. Both K3[VMo12O40]19H2O (1) and [N i (H2O)6][H3PMoVMoVI 11O40]230 H2O (2) were prepared in aqueous solution. Compound 1 crystallized in the space group Pm-3m, a=10.6513(1) Å, V=1208.4(3) Å3, Z=1. Compound 2 crystallized in the space group R-3 with a=b=13.9669(2) Å, c=42.0075(5) Å, V=7096.71(2) Å3, Z=3. The compound 1 contains a {K6VMo12O40} group in which six potassium ions form a regular {K6} octahedron. The heteropolyanion [VMo12O40]3– was capped by six potassium ions and enclosed by {K6} octahedron. A three-dimensional structure was formed by the buildup of {K3[VMo12O40]} n . Compound 2 contains a one-electron reduced heteropolyanion [H3PMoVMoVI 11O40]1–. Ni2+ coordinated by six water molecules as the counter cation balances the negative charge of the molecule.  相似文献   

3.
Two couples of new compounds templated by the polyanion [SiW12O40]4?,[Hbix][CuI(bix)]3[SiW12O40]·4H2O (1) and [CuII(H2O)(Hbix)2(bix)]2[CuII(H2O)2(Hbix)2(bix)][SiW12O40]3·4H2O (2) (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene), [CuI(bbi)]4[SiW12O40]·2H2O (3) and [CuII(bbi2)]2[SiW12O40] (4) (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) were hydrothermally synthesized, and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses and single X-ray diffraction. Compounds 1 and 2 were synthesized from the same reactants but exhibited distinct structures which could be ascribed to the different ratios of the reactant bix to CuII. In compound 1, the higher ratio of bix results in the transformation of the CuII to CuI, the [SiW12O40]4? templates direct the CuI–bix coordination polymers to form a 3D supramolecular framework with grid-like channels along two directions. The [SiW12O40]4? templates in compound 2 locate in the voids of the 3D supramolecular network constructed by CuII–bix coordination polymers, which exhibits the interdigitation fashion in both the formation of the 2D layer and the 3D framework. Compounds 3 and 4 were synthesized similar to 1 and 2, except for the change of bix to bbi. In compound 3, the CuI–bbi polymers form a supramolecular metal–organic host framework with rhombic channels in which the SiW12 templates reside. Compound 4 shows a framework with hexagonal channels constructed by CuII–bbi coordination polymers which accommodated the SiW12 templates.  相似文献   

4.
A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O(2,2'-bpy=2,2'-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2'-bpy)3] together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2'-bpy)3] via multiple C-H…O hydrogen bonds resulting in a dimer.  相似文献   

5.
Two polyoxometalate-templated nickel-Schiff-base compounds, {[Ni(L)2]2[PMo12O40][Cl] · 1.5DMF · H2O} n (1) and {[Ni(L)2]2[PMo12O40][Cl] · DMSO · CH3OH · 0.5H2O} n (2) (where L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), were synthesized in situ from Ni2+ and L in H2O/DMF/CH3OH or H2O/DMSO/CH3OH at room temperature and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The results of the single-crystal X-ray diffractions suggested that both compounds have the same packing of the Ni(II)-Schiff-base cation layer and Keggin anion layer. Thermogravimetric analyses suggested that two supramolecular compounds have similar thermal stabilities based on the same packing of the cation and anion layers.  相似文献   

6.
A new organometallic-inorganic hybrid compound {[Mn(L)2]2[PMo12O40][NO3] · 4CH3OH · 3H2O} n (I), where L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene) was synthesized in situ from [PMo12O40]3?, Mn2+ and L reaction in an H2O-DMSO-CH3OH mixture at room temperature, and the product was structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. Compound I is constructed from alternating layers of the metal-Schiff-base cation and Keggin anions based on electrostatic forces and hydrogen bond interactions.  相似文献   

7.
Two supramolecular compounds based on tungstoferrate [FeW12O40]5?, [FeII(2,2′-bipy)3]2[HFeW12O40] · 5H2O (1), and [Hpy]2[4,4′-H2bipy]6(H3O)[FeW12O40]3 · 11H2O (2) (py = pyridine, bipy = bipyridine) were synthesized hydrothermally and characterized structurally. The hydrogen bonds between polyoxoanions and water and the edge-to-face π–π interaction between [FeII(2,2′-bipy)3]2+ with a shortest C–C distance of 3.513 Å are the main forces to construct the 3-D architecture of 1. In 2, a 3-D supramolecular architecture is assembled by the tungstoferrate anions, protonated 4,4′-bipy cations, and water through hydrogen bonding. The variable-temperature magnetic susceptibilities indicate that 1 is paramagnetic with μ eff corresponding to one Fe(III) with spin-only contribution, showing that Fe in the coordination cations has a +II oxidation number and low spin state.  相似文献   

8.
Zuo  Jing-Lin  Gu  Zhao-Hui  Bai  Jun-Feng  Shen  Zhen  You  Xiao-Zeng 《Transition Metal Chemistry》1999,24(2):160-162
The charge transfer salt, (ET)5PVMo11O40·2H2O [ET=bis(ethylene)-dithiotetrathiafulvalene], was prepared by reducing the diamagnetic molybdovanadophosphoric heteropoly acid (H4PMo11VO40·nH2O, HMVP) with the organic donor ET. The u.v.-vis spectrum of the complex shows an electronic transfer band at 900nm. The i.r. and Raman spectra suggest that the ET donor molecules are all completely ionized. Magnetic measurements indicate the presence of antiferromagnetic interactions in the ET organic sublattice. The e.s.r. spectrum exhibits a VIV signal with g=1.9718 and a=57.5cm–1. Over the measured temperature range (75–300K), no significant interaction between the paramagnetic anion and the organic radical cation is observed.  相似文献   

9.
《Polyhedron》2003,22(14-17):1777-1782
(PPh4)2[Mn12O12(O2CCHCl2)16(H2O)4] (3) has been prepared by the two-electron reduction of [Mn12O12(O2CCHCl2)16(H2O)4] (2) using iodide. Crystallization from CH2Cl2/hexanes yields a mixture of two crystal forms, 3·4CH2Cl2·H2O (3a) and 36CH2Cl2 (3b), which are triclinic and monoclinic, respectively. They are both trapped valence 2Mn(II), 6Mn(III), 4Mn(IV). DC magnetization data for dried, unsolvated 3 in 1.80–4.00 K and 10–70 kG ranges were fit to give S=10, D=−0.28 cm−1, g=2.00. Frequency-dependent out-of-phase (χM) signals in AC susceptibility studies on crystalline sample of 3a and 3b combined with DC relaxation decay data were fit to the Arrhenius equation to give an effective energy barrier of Ueff=18.5 and 30.3 K, respectively. Magnetization vs. DC field sweeps on single crystals of 3a and 3b gave hysteresis loops containing steps due to quantum tunneling of magnetization (QTM). The step separations yielded ∣D∣/g values of 0.087 and 0.14 cm−1, and consequently U=20 and 39 K (for g=2) for 3a and 3b, respectively, suggesting that the differences in Ueff are primarily caused by changes to D. This work demonstrates the sensitivity of the magnetic properties of [Mn12]2− single-molecule magnets to subtle differences in their environment.  相似文献   

10.
A novel hybrid tungstocuprate ( Ⅱ ) [ Cu (2,2'-bpy) 3 ] 2 H4 [ CuW12O40 ] · 6H2O ( 2,2'-bpy = 2,2'-bipyfidine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [ CuW12O40 ]^6- and a pair of chiral complex cations [ Cu(2,2'-bpy) 3 ]^+ together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [ Cu (2,2'-bpy)3 ]^+v/a multiple C-H…O hydrogen bonds resulting in a dimer.  相似文献   

11.
[Co(phen)3]2[PMo12O40](OH)的水热合成及晶体结构   总被引:1,自引:0,他引:1  
利用水热合成法制备了Keggin结构阴离子有机一无机复合物[Co(phen)3]2[PMo12O40](OH),通过元素分析,红外光谱和X射线单晶衍射等对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.=1.97225(18)nm,b=1.81079(16)nm,c=2.5117(2)nm,β=100.5380(10)°,V=8.819O(14)nm^3,Z=4,R1=0.0587,wR2=0.1211.该化合物分子由一个多阴离子[PMo12O40]^3-,两个[Co(phen)3]^2+及一个羟基组成.  相似文献   

12.
Reaction of uranium salts with several lacunary polyoxotungstate anions yields four new heteropolyanion assemblies in which the uranium atoms occupy pentagonal bipyramidal coordination polyhedra. Treatment of A,-[SiW9O34]10– with UO2(NO3)2 leads to Na14[Na2(UO2)2(SiW9O34)2]38H2O (1, Monoclinic, P21/c, a=16.5719(8) Å, b=14.1689(7) Å, c=21.2528(10) Å, =111.6670(10)°, V=4786.6(4) Å3, Z=2) which proves to be isostructural with the analogous derivative of [PW9O34]9– reported previously. Solutions of 1 exhibit the 5-line W-NMR spectrum expected for the structure of C i point symmetry. The salt (NH4)17[(UO2)3(H2O)4As3W26O94]16H2O (2, Orthorhombic, Pnma, a=40.1747(2) Å, b=18.25840(10) Å, c=18.0817(2) Å, V=13263.4(2) Å3, Z=4) was isolated in 64% yield from a reaction of UO2(NO3)2 with B,-[AsW9O33]9–. The structure of the anion in 2 has C s symmetry and contains one -AsW9O33 and two novel -AsW8O30 units linked by the UO2+ 2 groups; an additional WO6 links the two AsW8 fragments. Spectrophotometric titration of UCl4 with the sodium salt of [As4W40O140]28– indicated the formation of a 4:1 U:As4W40 complex. During attempts to isolate a crystalline product from this reaction the uranium became oxidized and a guanidinium salt of [Na(UO2)3(OH)(H2O)6As4W40O140(WO)]18– (3, Orthorhombic, Fdd2, a=54.848(3) Å, b=80.809(4) Å, c=20.2874(2) Å, V=89919(7), Z=16) was isolated. The partially disordered structure of 3 shows the S2 and adjacent sites of the lacunary As4W40 anion to be occupied by three UO5 and one WO5 polyhedra. A tetrameric assembly of -SiW10 units linked by UO2+ 2 groups occurs in [{M(OH2)}4(UO2)4(OH)2(SiW10O36)4]22– (lithium salt, M=Na, 4a, tetragonal, P42/nmc, a=b=26.5285(2) Å, c=15.0463(2) Å, V=10589.0(2) Å3, Z=2; sodium-potassium salt, M=K, 4b, orthorhombic, Fddd, a=24.180(5) Å, b=31.696(6) Å, c=58.012(12) Å, V=44460(15) Å3, Z=8). Tungsten-183 NMR spectra show the slow transformation of the expected 5-line (1:1:1:1:1) spectrum of 4a to a new species giving a 6-line spectrum (2:2:2:1:2:1). The latter complex has not been successfully isolated.  相似文献   

13.
Xu  Mei-Xian  Lin  Shen  Xu  Li-Min  Zhen  Si-Lin 《Transition Metal Chemistry》2004,29(3):332-335
The title compound H3[PMo12O40]· 3C2H6O was prepared and characterized by X-ray crystallography, its i.r. spectrum, cyclic voltammetry and e.s.r. spectra. The anion of the title compound is a Keggin-type heteropoly structure based upon a central PO4 tetrahedron surrounded by 12 MoO6 octahedra arranged in four groups of three edge-shared octahedra Mo3O13. Weak hydrogen bonds exist between the organic solvent molecules and the heteropoly anion. The catalytic activity of the title compound was determined by the synthesis of butyl acetate. The conversion of n-BuOH reached 93.3% and the yield of MeCO2Bu-n was 92.0% when the ratio of MeCO2H to n-BuOH, catalyst amount, reaction time, reaction temperature were 2:1, 0.24% of the reactants (50 mg), 2.0 h and 115 120 °C, respectively.  相似文献   

14.
Complexes with antimony-containing anions, [Ph3MeP] + 2 [SbI5]2? (I), [Ph3MeP] + 2 [Sb3I12]3? (II), [Ph3MeP] + 3 [Sb3I12]3? · Me2C=O (III), and [Ph3MeP] + 3 [Sb2I9]3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI3 groups is bound to the central Sb atom through two μ2- and one μ3 iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.  相似文献   

15.
合成了一个新的三维超分子化合物[Ni(DMF)6]2[SiMo12O40]·H2O,通过红外光谱、X射线单晶衍射和热重分析等手段对其结构进行了表征.单晶结构解析结果表明,标题化合物属于三方晶系,船空间群,晶胞参数为:a=1.5902(4)nm,b=1.5902(4)nm,c=3.2281(17)nm,V=7.069(4)nm^3,Z=3,Dc=1.994g/cm^3,μ=2.032mm^-1.F(000):4146,R1=0.0516,ωR2=0.1453.配合物中镍离子采用6配位的八面体配位构型,晶体堆积中通过多种分子间氢键作用形成三维网状结构.  相似文献   

16.
Two coordination polymers (CPs) based on Keggin-type [SiW12O40]4 (SiW12), [Zn2(bpy)2(SiW12O40)(DMF)8solvent (1) and [Zn2(bpy)(SiW12O40)(DMA)8]·2DMA (2) (bpy = 4,4′-bipyridine, DMF?=?N,N′-dimethylformamide; DMA?=?N,N′-dimethylacetamide), have been solvo-thermally synthesized and characterized by single crystal X-ray diffraction, powder X-ray diffraction, IR spectra, elemental analyses and thermogravimetric analyses. Both 1 and 2 are synthesized under similar conditions except DMF and DMA were used as the solvents for 1 and 2, respectively. Structural studies reveal that the supramolecular framework of 1 contains pumpkin-like voids, while 2 has a non-porous supramolecular framework. These results show that solvents play an important role in construction of the POM-based CPs. The luminescent properties for 1 and 2 have also been investigated.  相似文献   

17.
18.
Three new inorganic-organic composite polyoxotungstates [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]-4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847(3), b = 21.597(2), c = 20.1179(19)A, V= 12099(2)A^3, Z= 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1^- with a = 12.31150(10), b = 16.1954(4), c = 19.36290(10)A, α = 99.366(11), β =105.168(8), γ = 111.836(8)°, V = 3309.98(9)A3, Z = l, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5)A, β = 102.338(5)°, V= 4103(2)A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1-3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.  相似文献   

19.
Xianjun Lang  Zhen Li 《合成通讯》2013,43(10):1610-1616
Ionic liquid–modified polystyrene resin beads were demonstrated to be an appropriate support for polyoxometalate. In this heterogeneous catalytic system, alcohols can be efficiently oxidized to corresponding carbonyl groups with H2O2 in CH3CN. The catalyst can be easily recovered by filtration and recycled without apparent loss of catalytic performance.  相似文献   

20.
采用密度泛函方法,在DND基组水平上,对[GeMo12O40]^4-杂多阴离子最常见的α和β异构体进行了几何构型优化,得到了与X射线晶体衍射实验结果相一致的结构参数,并在此基础上进行了振动频率分析,得到了杂多阴离子的电子结构、热力学特性和振动光谱,通过定义α,β异构体异构化反应的Gibbs函变△Gα-β与温度的关系,研究了这两种异构体的相对稳定性.结果表明:低温时α异构体更稳定,高温时β异构体更稳定些,550K左右为转变点.振动频率分析得到2种异构体的最强峰位于4个频率位置,分别指认为vax(Mo-Od),vas(Mo-Od),vas(Mo-Oc-Mo),vas(Ge-Oa),vas(Mo-Ob-Mo)振动,与红外光谱(IR)的特征振动峰相对应,观察到了特征频率的振动模式,从理论计算角度说明了Rocchiccioli—Deltcheff关于振动模式的设想是合理的.  相似文献   

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