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1.
Three new drug molecules modifying Keggin polyoxometallate compounds have been synthesized under hydrothermal conditions and structurally characterized by routine techniques. Single-crystal X-ray diffraction analysis shows that compound 1 is constructed by a Keggin cluster and two [Cu(PPA)2] drug complexes, formulated as [Cu(PPA)2]2·[PW12O40]·6H2O. Compound 2 consists of a Cd substituted Keggin cluster [PW11CdO39] and five isolated HPPA drug molecules, formulated as [HPPA]5·[PW11CdO39]·2H2O. Compound 3 consists of a full oxidised Keggin [PW12O40] cluster and three isolated HPPA drug molecules, formulated as [HPPA]3·[PW12O40]·2H2O. Additionally, the antitumor activity of the three new compounds and their parent components in vitro were studied by a MTT experiment. The results show that introduction of TM-PPA/PPA into the polyoxoanion surface could increase their antitumor activity and make the compounds penetrate into the cells easily. Furthermore, the antitumor activity of the compounds can be modulated by their different structures.  相似文献   

2.
Two new organic-inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV-vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy)3]2[H2W12O40]·8H2O (1), the [Ru(bpy)3]2+ (bpy=2,2′-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H2W12O40]6− linked through {KO7} and {NaO6} polyhedra, while in K6[Ru(pzc)3]2[SiW12O40]•12H2O (2), the [Ru(pzc)3] (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW12O40]4− clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion?π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.  相似文献   

3.
Summary The half Wells-Dawson structure complex Na9PW8-MoO34·11H2O has been prepared by reaction of Na2WO4·2H2O, Na2MoO4·2H2O and KH2PO4 in water. A series of transition metal substituted heteropolyoxometalate complexes with ternary Keggin structures of the general formula [TBA]3H n [PW9MoM2O38 (H2O)2]·3C3H6O (TBA = tetrabutylammonium; n = 2, M = Fe3+; n = 4, M = Mn2+,Co2+,Cu2+or Zn2+), have been synthesized using Na9PW8MoO34·11H2O and the transition metal nitrate as the starting materials in aqueous solution. The compounds were characterized by elemental analyses and spectroscopy. X.p.s. data indicate that the binding energies of all the elements in the title compounds are lower than those in similar compounds. The magnetic susceptibilities of the compounds reveal antiferromagnetic properties.  相似文献   

4.
A structurally distinct, multi-copper(II)-substituted silicotungstate K3H4Cu0.5{Cu[Cu7.5Si2W16O60(H2O)4(OH)4]2} · 9H2O (1) has been synthesized and characterized by FT-IR spectroscopy, elemental analysis, variable-temperature magnetic measurements, electron spin resonance, and X-ray diffraction. Green crystalline plates of 1 were obtained by the reaction of K8[γ-SiW10O36] · 12H2O with 8 equiv. of Cu(II) in a 50% ethylene glycol solution. A cationic copper center connects the terminal oxygen atoms of neighboring polyanions, resulting in a one-dimensional structure. Magnetic susceptibility measurements indicate weak ferromagnetic superexchange between the Jahn–Teller-distorted S = 1/2 Cu(II) centers.  相似文献   

5.
Four tetrahydrofuran-2,3,4,5-tetracarboxylato bridged copper(II) coordination polymers with alkali metals, Na2[Cu(H2O)(THFTC)]·5H2O 1, K2[Cu3(H2O)2(THFTC)2]·9H2O 2, Rb2[Cu3(H2O)2(THFTC)2]·6H2O 3 and Cs2[Cu3(H2O)2(THFTC)2]·6H2O 4 (H4THFTC = tetrahydrofuran-2,3,4,5-tetracarboxylic acid) were prepared from reactions of Cu(NO3)2·3H2O, tetrahydrofuran-2,3,4,5-tetracarboxylic acid and alkali hydroxide or carbonate at pH 5.0–6.0 under ambient conditions. Compound 1 features 2D (33·43·54) topological layers generated from six-coordinated Cu2+ cations interlinked by (THFTC)4− anions, and the resulting layers are ecliptically stacked along [1 0 0] direction to form lozenge-shaped and octagonal channels filled with Na+ ions and lattice H2O molecules. In 2–4, both penta- and hexa-coordinated copper(II) ions are bridged by tetracarboxylate anions to form negatively charged 2D layers formulated as 2[Cu(H2O)2L3/2]2− with the corresponding alkali metal cations (K+, Rb+ or Cs+ ions) and hydrogen bonded lattice H2O molecules sandwiched between them. Additionally, the results about i.r. spectroscopic, thermal characterizations and magnetic properties are presented.  相似文献   

6.
Summary The new complexes K2[Ni(H2heo)2]·3H2O, K2[Pd-(H2heo)2], K2[Cu(heo)]·3H2O and [Cu2(heo)·2H2O] {heo = [(CONCH2CH2O)2]4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN4 coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu2(heo)·2H2O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H2O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.  相似文献   

7.
Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)2]2{[Cu(phen)]2 [SiMo12O40(VO)2]} (1), {[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2 [GeMo12O40(VO)2]}·3H2O (2) and {[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2 [PMo12O40(VO)2]}·2.5H2O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo12O40(VO)2] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo12O40(VO)2]2− linked to two [Cu(phen)]+ complexes with two [Cu(phen)2]+ countercations. Compound 2 contains two bicapped Keggin anions [GeMo12O40(VO)2]4−, one linked to two [Zn(phen)2(H2O)]2+ cations and the other one linked to two [Zn(phen)2]2+ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo12O40(VO)2]4− connected by [Co(phen)2]2+ cations. Discrete bicapped Keggin anions [PMo12O40(VO)2] linked to two [Co(phen)2(OH)]+ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.  相似文献   

8.
Two new compounds based on polyoxometalates (POMs) and the quinolone antibacterial drug pipemidic acid (HPPA), {[Ni(PPA)2]H4[SiW12O40]}·HPPA·3H2O (1), and {[Zn(PPA)2]2H4[SiW12O40]}·3H2O (2), have been synthesized under hydrothermal conditions and structurally characterized by routine technique. Single-crystal X-Ray diffraction analysis shows that compound 1 is constructed by Keggin clusters grafted by binuclear nickel clusters, isolated HPPA and water molecules, while compound 2 consists of Keggin clusters grafted by binuclear zinc clusters and water molecules. Due to the selection of different transition metal (TM) ions, compounds 1 and 2 exhibit different structures and antitumor activities. Compound 1 possesses 0D structure and shows no antitumor activities. However, compound 2 possesses 1D structure and exhibits higher antitumor activities than its parent compound. The results show that introduction of different TM-PPA moieties onto the polyoxoanion surface can affect not only the final structures but also their antitumor activities.  相似文献   

9.
Two molecular double-supporting polyoxotungstates [SiW12O40{M(phen)2H2O}2] · nH2O (phen = 1,10′-phenanthroline, M = Mn 1, n = 2; M = Co 2, n = 3) were synthesized hydrothermally and characterized by elemental analyses, IR, TG, and X-ray single-crystal diffraction. The variable-temperature magnetic susceptibilities were measured at 2–300 K. The double-supporting polyoxotungstate molecule consists of a Keggin-type dodecatungstosilicate anion and a pair of transition metal complex fragments which are covalently linked to opposite sides of the Keggin anion. The transition metal ion locates in the center of a distorted octahedron. Multiple H-bonding interactions are observed between the coordinated waters of the transition metal complex fragments and terminal oxygen atoms of Keggin units and also between the bridging oxygen atoms of Keggin units and the lattice waters, which creates one-dimensional chains or two-dimensional layers. Between the layers or chains there are weak CH···O hydrogen bonding interactions and van der Waals forces. The molecular double-supporting polyoxotungstosilicate begins to decompose at ca. 500 °C. The variable-temperature magnetic behavior of 1 shows weak antiferromagnetic characteristics with a small value of θ = −0.289 K.  相似文献   

10.
Inorganic-organic hybrid frameworks, namely [Ce(H2O)3(pdc)]4[SiW12O40]·6H2O 1, [M(H2O)4(pdc)]4[SiW12O40]·2H2O (M=Ce for 2a, La for 2b, Nd for 2c; H2pdc=pyridine-2,6-dicarboxylic acid) were assembled through incorporation of Keggin-type heteropolyanion [SiW12O40]4− within the voids of lanthanides-pdc network as pillars or guests under hydrothermal condition. Single-crystal X-ray analyses of these crystals reveal that compound 1 presents 3D pillar-layered framework with the [SiW12O40]4− anions located on the square voids of the two-dimensional Ce-pdc bilayer. Compounds 2a-c are isostructural and constructed from 3D Ln-pdc-based metal-organic framework (MOF) incorporating noncoordinating guests Keggin structure [SiW12O40]4−. Solid-state properties of compounds 1 and 2a-c such as thermal stability and photoluminescence have been further investigated.  相似文献   

11.
The reaction of Na10[A-α-SiW9O34] · 18H2O with CuCl2 · 2H2O in the participation of ethylenediamine (En) under hydrothermal conditions resulted in a 2D organic-inorganic hybrid monocopper(II)-substituted Keggin silicotungstate [Cu(En)2(H2O)]2[Cu(En)2]4[Si2Cu2W22O78] · 7H2O (I), which was structurally characterized by elemental analyses, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Single crystal structural analysis shows that adjacent monocopper(II)-substituted Keggin silicotungstate [Si2Cu2W22O78]12? dimeric subunits are interconnected by sharing terminal oxygen atoms to make the 1D polymeric linear chain and neighboring chains are combined with each other through [Cu(En)2]2+ connectors giving rise to an interesting 2D organic-inorganic hybrid sheet architecture with a 4-connected topology. To our knowledge, I is the rare organic-inorganic hybrid 2D polyoxometate constructed by mono-transition-metal substituted Keggin silicotungstate dimeric subunits. The photocatalytic measurement illustrates that I can to some extent inhibit the photodegradation of rhodamine-B.  相似文献   

12.
Three new extended frameworks built from paratungstate and transition metals have been synthesized and characterized. In the compound Na8[{Cd (H2O)2}(H2W12O42)]·32H2O (1), two neighboring paratungstate-B ions [H2W12O42]10− are linked by [Cd(H2O)2]2+ units, leading to the formation of infinite one-dimensional (1D) anion chain [{Cd(H2O)2}(H2W12O42)]n8n. The anion [{Co(H2O)3}{Co(H2O)4}(H2W12O42)]n6n of the compound Na6[{Co(H2O)3}{Co(H2O)4}(H2W12O42)]·29H2O (2) shows a layer-like (2D) structure in which paratungstate-B units are linked by CoO6 octahedra, while the anion [{Co(H2O)3}3(H2W12O42)]n4n of the compound (H3O+)3[{Na(H2O)4}{Co(H2O)4}3(H2W12O42)]·24.5H2O (3) is a three-dimensional (3D) anionic polymer that consists of paratungstate-B units linked by CoO6 octahedra. Compound 3 can reversibly adsorb and desorb water molecules leading to the color reversibly change from pink to violet. The preliminary magnetic measurement and electrochemical properties of compounds are performed. The crystal structure of unexpected product Na4[NiW6O24H6]·13H2O (4) is described here for the rare report of crystal structure information on the Anderson-type polyoxotungstate which has nickel as a heteroatom.  相似文献   

13.
The electrochemical behaviour of the copper-substituted Keggin-type and sandwich-type polyoxotungstate anions of the compounds α-[(C4H9)4N]4H[PW11CuIIO39] and α-B-[(C4H9)4N]7H3[CuII4(H2O)2(PW9O34)2] was studied by cyclic voltammetry in acetonitrile. In both cases two copper 1-electron reduction waves were detected in the cathodic scan. The first one was due to the reduction of one CuII to CuI in the polyoxoanion and the second one to the consecutive reduction of the preformed CuI to Cu0, with the consequent deposition/adsorption of the ejected metal atom at the glassy carbon electrode surface. In the anodic scan, Cu0 was re-oxidised with regeneration of the initial copper(II) complexes, via a CuI intermediate. The observed two-step reduction of copper(II) to copper(0) and the formation of intermediate species containing copper(I) is here reported for the first time for copper substituted polyoxotungstates. The co-ordination of the acetonitrile molecules to the copper ions must play a role in the formation of the copper(I) species, which are not detected in aqueous solution.  相似文献   

14.
The hydrothermal reaction of H2MoO4, copper acetate and imidazole in water gave rise to the title compound [Cu(imi)2]4[(imi)2Mo8O26]·4H2O (1) as brown crystals. Single X-ray crystal analysis reveals that 1is built up from imidazole coordinated copper fragments and imidazole coordinated octamolybdate units. These dodec-nuclear clusters are assembled into one-dimensional chain through weak copper(I)–copper(I) interactions, and further attached into three-dimensional network in the packing via complex hydrogen bonding.  相似文献   

15.
An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2]·H2O (1), [CuLNCS]·½H2O (2), [CuLNO3]·½H2O (3), [Cu(HL)Cl2]·H2O (4), [Cu2(HL)2(SO4)2]·4H2O (5), [CuLClO4]·½H2O (6), [CuLBr]·2H2O (7), [CuL2]·H2O (8) and [CuLN3]·CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2-y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.  相似文献   

16.
The synthesis, reduction, optical and e.p.r. spectral properties of a series of new binuclear copper(II) complexes, containing bridging moieties (OH, MeCO2 , NO2 , and N3 ), with new proline-based binuclear pentadentate Mannich base ligands is described. The ligands are: 2,6-bis[(prolin-1-yl)methyl]4-bromophenol [H3L1], 2,6-bis[(prolin-1-yl)methyl]4-t-butylphenol [H3L2] and 2,6-bis[(prolin-1-yl)methyl]4-methoxyphenol [H3L3]. The exogenous bridging complexes thus prepared were hydroxo: [Cu2L1(OH)(H2O)2] · H2O (1a), [Cu2L2(OH)(H2O)2] · H2O (1b), [Cu2L3(OH)(H2O)2] · H2O (1c), acetato [Cu2L1(OAc)] · H2O (2a), [Cu2L2(OAc)] · H2O (2b), [Cu2L3(OAc)] · H2O (2c), nitrito [Cu2L1(NO2)(H2O)2] · H2O (3a), [Cu2L2(NO2)(H2O)2] · H2O (3b), [Cu2L3(NO2)(H2O)2] · H2O (3c) and azido [Cu2L1(N3)(H2O)2] · H2O (4a), [Cu2L2(N3)(H2O)2] · H2O (4b) and [Cu2L3(N3)(H2O)2] · H2O (4c). The complexes were characterized by elemental analysis and by spectroscopy. They exhibit resolved copper hyperfine e.p.r. spectra at room temperature, indicating the presence of weak antiferromagnetic coupling between the copper atoms. The strength of the antiferromagnetic coupling lies in the order: NO2 N3 OH OAc. Cyclic voltammetry revealed the presence of two redox couples CuIICuII CuIICuI CuICuI. The conproportionality constant K con for the mixed valent CuIICuI species for all the complexes have been determined electrochemically.  相似文献   

17.
在水热条件下合成了一个新的化合物{[Cu4(PMo12O40)(H2O)5(H2bpdc)(Hbpdc)(bpdc)2].6H2O}n(H2bpdc=2,2′-联吡啶-3,3′-二羧酸),并用元素分析、IR、TG和X-射线衍射等手段进行了表征。结果表明本化合物的晶体结构中,最小不对称单元包含1个[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+阳离子,1个[PMo12O40]3-阴离子和6个结晶水分子。Cu(Ⅱ)与相邻[PMo12O40]3-的桥氧原子配位,形成一维链状结构。电化学研究表明,化合物存在三步氧化还原过程。  相似文献   

18.
The X-ray crystal structures of two ciprofloxacin compounds, viz. [Cu(cfH)2(Cl)2] · 2MeOH · 6H2O (2) and [Cu(cfH)(phen)Cl]BF4 · 4H2O (3) are reported. Complex (2) has a distorted octahedral geometry, whereas for the nitrogen adduct (3) a distorted square–pyramidal geometry is seen. Significant enhancement in the antimycobacterial activity of the copper conjugates correlates with their copper redox couples (Cu2+ /Cu+) probably due to its relevance to intracellular accumulations and subsequent role in generating oxidative stress.  相似文献   

19.
Three new high dimensional CuI/Ag-pz porous coordination polymers (PCPs) with different Keggin polyoxometalate templates have been hydrothermally synthesized: [CuI5(pz)6Cl][HPMoVI10MoV2O40] (1) [Ag5(pz)7(BW12O40)] (2) and [CuI5(pz)6H(H2W12O40)]·4H2O (3) (pz=pyrazine). The choice of the particular Keggin POM templates is shown to influence the structural properties of the Cu/Ag PCPs. Compound 1 shows a Cl-bridged Cu-pz-Cl double layer, between which two kinds of [HPMoVI10MoV2O40]4−(PMo12) polyanions are located. Compound 2 presents a 3D Ag-pz framework with parallelogram-like voids, into which BW12O405− (BW12) Keggin ions are incorporated. Compound 3 contains a Cu-pz cationic layer framework, between which are located [H(H2W12O40)]5− (W12) Keggin ions. Primary photocatalytic experiment indicates that compound 1 presents excellent photocatalytic activity. The photoluminescence properties and electrochemistry properties of the compounds are also discussed.  相似文献   

20.
Summary Eight aluminium and gallium heteropoly undecatungstometalate complexes of general formula Kn[M(H2O)-XW11O39]·nH2O, where M=AlIII, GaIII, and X=CrIII, FeIII, CoII or CuII, have been prepared and characterized by elemental analysis, cation exchange i.r., u.v., x-ray powder diffraction and by thermal analyis. The compounds are stable in acidic solution. I.r., u.v. spectra and x-ray diffraction studies show that the structure of the compounds derives from the Keggin structure. Their thermostability is higher than that of the homologous dodecatungstometalates.  相似文献   

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