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1.
A variety of novel copper complexes were synthesized and characterized of the formulae [Cu(L1)(OAc)], [CuL2(H2O)], [CuL3(H2O)], [CuL4(OAc)], [CuL5(H2O)] [CuL6], [CuL7], [CuL8](OAc) and [CuL9], where L1 L9 represents Schiff base ligands [derived by the condensation of 5‐hydroxyflavone with 4‐aminoantipyrine (L1), o‐aminophenol (L2), o‐aminobenzoic acid (L3), o‐aminothiazole (L4), thiosemicarbazide (L5), 4‐aminoantipyrine‐o‐aminophenol (L6), 4‐aminoantipyrine‐o‐aminobenzoic acid (L7), 4‐aminoantipyrine‐o‐aminothiazole(L8) and 4‐aminoantipyrine‐thiosemicarbazide (L9)]. The spectral and magnetic results of the Cu(II) complexes exhibit square planar geometry. The DNA binding properties of copper complexes were studied by using electronic absorption spectra, viscosity and thermal denaturation experiments. The results show that the complexes were interacting with calf thymus (CT DNA). The in vitro antimicrobial activities of the investigated compounds were tested against the bacterial species and fungal species. Superoxide dismutase and antioxidant activities of the copper complexes have also been studied. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

2.
Liu  Jie  Lu  Tong-Bu  Deng  Hong  Ji  Liang-Nian  Qu  Liang-Hu  Zhou  Hui 《Transition Metal Chemistry》2003,28(1):116-121
Two macrocyclic copper(II) complexes, [CuL1](ClO4)2 (L1 = 2,6,9,13-tetraparacyclophane, a Schiff base) and [CuL2]Cl2 [L2 = 3,10-bis(2-benzyl)-1,3,5,8,10,13-hexaazacyclotetradecane] have been prepared and characterized by elemental analysis, u.v.–vis., i.r. and mass spectra. Absorption, fluorescence, circular dichroic spectra and viscosity experiments have been carried out on the interaction of the two complexes with calf thymus CT DNA. The results suggest that both complexes can bind to CT DNA by intercalation via the aromatic moiety ring in the macrocycle into the base pairs of DNA. [CuL1](ClO4)2 binds to CT DNA more strongly than [CuL2]Cl2. The position of the aromatic ring in the macrocycle plays an important role in deciding the extent of binding of the complexes to DNA. Significantly, the complexes have been found to be single-strand DNA cleavers in the presence of H2O2 or/and 2-mercaptoethanol.  相似文献   

3.
Two new potentially octadentate N2O6 Schiff-base ligands 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)phenoxy)phenylimino)methyl)-6-methoxyphenol H2L1 and 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy)-4-tert-butylphenoxy)phenylimino)methyl)-6-methoxyphenol H2L2 were prepared from the reaction of O-Vaniline with 1,2-bis(2′-aminophenoxy)benzene or 1,2-bis(2′-aminophenoxy)-4-t-butylbenzene, respectively. Reactions of H2L1 and H2L2 with copper(II) and zinc(II) salts in methanol in the presence of N(Et)3 gave neutral [CuL1]?·?0.5CH2Cl2, [CuL2], [ZnL1]?·?0.5CH2Cl2, and [ZnL2] complexes. The complexes were characterized by IR spectra, elemental analysis, magnetic susceptibility, ESI–MS spectra, molar conductance (Λm), UV-Vis spectra and, in the case of [ZnL1]?·?0.5CH2Cl2 and [ZnL2], with 1H- and 13C-NMR. The crystal structure of [ZnL1]?·?0.5CH2Cl2 has also been determined showing the metal ion in a highly distorted trigonal bipyramidal geometry. The electrochemical behavior of H2L2 and its Cu(II) complex, [CuL2], was studied and the formation constant of [CuL2] was evaluated using cyclic voltammetry. The logarithm value of formation constant of [CuL2] is 21.9.  相似文献   

4.

Abstract  

Three new transition metal complexes [CuL2Cl2], [NiL2Cl2], and [ZnL2Cl2], where L = Schiff base derived from isatin (1H-indole-2,3-dione) and tyramine (4-(2-aminoethyl)phenol), have been synthesized and characterized spectroscopically. The binding properties of these complexes with calf thymus DNA have been investigated by use of electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry, and molecular docking analysis. Moreover, these complexes have been found to promote the cleavage of pUC19 DNA from the supercoiled form I to the open circular form II in the presence of hydrogen peroxide. The newly synthesized compounds were screened for antibacterial activity and subjected to molecular docking studies for inhibition of the enzyme Staphylococcus aureus sortase-A, which is a novel target for antibacterials.  相似文献   

5.
An axially elongated copper(II) complex, CuL1Cl2, has been obtained by reaction of copper(II) chloride with a 17-membered N,O-donor macrocyclic ligand (L1). In an attempt to prepare the complex from copper(II) perchlorate, crystals of L1 suitable for X-ray were obtained as its diperchlorate salt, [H2L1][ClO4]2. Further reaction of CuL1Cl2 with LiTCNQ and Et3NH(TCNQ)2 furnished the charge transfer copper(I) complexes CuL1(TCNQ)2·3H2O and CuL1(TCNQ)3, with TCNQ carrying partially reduced charge. The presence of a diamagnetic metallic centre was confirmed by EPR and magnetic measurements.  相似文献   

6.
《Polyhedron》1999,18(8-9):1141-1145
Exchange reactions of trans-[PdXPh(SbPh3)2] (1) (X=Cl or Br) with ligands L in refluxing dichloromethane give the palladium phenyl complexes [PdXPhL2] (X=Cl, L=PPh3, AsPh3, L2=2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (dmbipy), 1,10-phenanthroline (phen); X=Br, L=PPh3, L2=bipy). Treatment of the complexes with bis(diphenylphosphino)methane (dppm) in refluxing dichloromethane gives [PdXPh(dppm]2. These complexes have been characterised by microanalysis, IR and 1H NMR spectroscopic data together with single crystal X-ray determinations of the phenyl palladium complexes, trans-[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdBrPh(dppm)]2.  相似文献   

7.
Two polypyridyl ligands 6-fluro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (FIPC), 6-chloro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (ClIPC) polypyridyl ligands and their Ru(II) complexes [Ru(bipy)2FIPC]2+(1), [Ru(dmb)2FIPC]2+(2), [Ru(phen)2FIPC]2+(3), [Ru(bipy)2ClIPC]2+(4), [Ru(dmb)2ClIPC]2+(5) and [Ru(phen)2ClIPC]2+(6) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine and phen = 1,10-phenanthroline) have been synthesised and characterised by elemental analysis, Mass spectra, IR, 1H and 13C-NMR. The DNA-binding of the six complexes to calf-thymus DNA (CT-DNA) has been investigated by different spectrophotometric, fluorescence and viscosity measurements. The results suggest that 1–6 complexes bind to CT-DNA through intercalation. The variation in binding affinities of these complexes is rationalised by a consideration of electrostatic, steric factors and nature of ancillary ligands. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen (1O2) plays a significant role in the cleavage mechanism of Ru(II) complexes. Thereby, under comparable experimental conditions [Ru(phen)2FIPC]2+(3), [Ru(phen)2ClIPC]2+(6) cleaves DNA more effectively than 1, 2, 4 and 5 complexes do. The Ru(II) polypyridyl complexes (1–6) have been screened for antimicrobial activities.  相似文献   

8.
The coordination compounds of copper(II) chloride and bromide with 1,2,4-triazole (L1) and 4-amino1,2,4-triazole (L2), CuL1Hal2 and CuL2Hal2, possess interesting magnetic properties [1, 2]. For example, at very low temperatures CuL1Cl2 and CuL1Br2 are ferromagnets [2](T c ≈ 3.3 and 6.5 K, respectively). To explain the magnetic behavior of copper(II) halide complexes with the above nitrogen heterocycles it is generally assumed that the complexes are polynuclear chain compounds in which the copper atoms are bridged by two halogen ions and bridging bidentate heterocycle molecules (coordination of N1 and N2 atoms). This hypothesis is made on the basis of the X-ray diffraction analysis of CuL1Cl2 [3]. It is interesting to perform an X-ray diffraction study of CuL2Cl2 and CuL2Br2; this is important for obtaining reliable magnetostructural correlations for this group of compounds. In this study, we investigated single crystals of the complexes; this demanded choosing special conditions of synthesis, which differ from the conditions suggested for the synthesis of polycrystals in [1]. In this communication we report on the results of synthesis and X-ray diffraction analysis of the single crystals of the coordination compound CuL2Cl2. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 1, pp. 207–212, January–February, 1997.  相似文献   

9.
Few novel mixed ligand copper(II) complexes of the type [Cu(L)(Cl)2(H2O)], [Cu(L)2]Cl2, [Cu(L)L1] and [Cu(L)(phen)H2O]Cl2 (where L is the ligand obtained from the condensation of N-(2-aminoethyl)-1,3-propanediamine with m-nitrobenzaldehyde (La)/o-chlorobenzaldehyde (Lb)/benzaldehyde (Lc)/p-methoxybenzaldehyde (Ld)/p-hydroxybenzaldehyde (Le)/furfuraldehyde (Lf)/pyrrole-2-carboxaldehyde (Lg); L1 is another ligand obtained from the condensation of anthranilic acid with salicyaldehyde; phen = 1,10-phenanthroline) have been synthesized and characterized by the spectral and analytical techniques. From these data, it is found that the ligands adopt distorted octahedral geometry on metalation with Cu(II) ion. The XRD data indicate that the complexes are polycrystalline with nanosized grains. The SEM images of [Cu(La)phen(H2O)]Cl2 and [Cu(Lf)2]Cl2 complexes show that they have leaf and cauliflower like morphology. The in vitro biological screening effects of the investigated compounds have been tested against the bacteria such as Escherichia coli, Klebsiella pneumoniae, Salmonella typhi, Pseudomonas aeruginosa and Staphylococcus aureus and fungi such as Aspergillus niger, Rhizopus stolonifer, Aspergillus flavus, Rhizoctonia bataicola and Candida albicans by the well diffusion method. A comparative study of MIC values of the Schiff base ligands and their complexes indicates that the complexes exhibit higher antimicrobial activity than the free ligands. An electrochemical study of the copper complexes containing electron withdrawing substituted ligands reveals that they prefer to bind to DNA in Cu(II) rather than Cu(I) oxidation state.  相似文献   

10.
Twenty new complexes were synthesized by reacting Co(II), Cu(II), Zn, Cr(III), Fe(III), Cd and Ag salts with 3,3-dimethyl-1-(3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline (L1), spiro{cyclohexane-1,3"-[1-(1-phenyl-3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline]} (L2), and 3,3-dimethyl-1-(1-phenyl-3-methylpyrazole-5-onilidene-4)-1,2,3,4-tetrahydroisoquinoline (L3). These compounds were studied by IR and electronic absorption spectroscopy. The type of coordination of their ligands was discussed on the basis of the results obtained and X-ray diffraction data for L3 and [CuL2 2 Cl2] · 2L2 obtained previously.  相似文献   

11.
Complexation of FeII and FeIII with azaheterocyclic ligands L (L = phen or bipy) were studied in the presence and in the absence of boron cluster anions [BnHn]2– (n = 10, 12). The reactions were carried out in air at room temperature in organic solvents and/or water. In all the solvents used, well known [FeL3]An (An = 2Cl or SO42–) ferrous complexes were formed from FeII salts. Composition of ferric complexes with L ligands depends on the nature of solvent: either dinuclear oxo‐iron(III) chlorides [L2ClFeIII–O–FeIIIL2Cl]Cl2 or ferric ferrates(III) [FeIIIL2Cl2][FeIIICl4], or [FeIIIL2Cl2][FeIIICl4L] were isolated from FeIII salts. Introduction of the closo‐borate anions to a Fe3+(or Fe2+)/L/solv. mixture stabilizes ferrous cationic complexes [FeL3]2+ in all the solvents used: only ferrous [FeL3][BnHn] (n = 10, 12) complexes were isolated from all the reaction mixtures in the presence of boron cluster anions.  相似文献   

12.
Two new potentially hexadentate Schiff bases, [H2L1] and [H2L2], were prepared by condensation of 2-(3-(2-aminophenoxy)naphthalen-2-yloxy)benzenamine with 3,5-di-tert-butyl-2-hydroxy benzaldehyde and o-vanillin, respectively. Reaction of these ligands with cobalt(II) chloride, copper(II) perchlorate, and zinc(II) nitrate gave complexes ML. The ligands and their complexes have been characterized by a variety of physico-chemical techniques. The solid and solution state investigations show that the complexes are neutral. Molecular structures of [CuL1], [CoL1]?·?C7H8, and [ZnL2]?·?CH3CN, which have been determined by single-crystal X-ray diffraction, indicate that [CuL1] and [ZnL2]?·?CH3CN display distorted square planar and distorted trigonal-bipyramidal geometry, respectively; the geometry around cobalt in [CoL1]?·?C7H8 is almost exactly between trigonal bipyramidal and square pyramidal. The synthesized ligands and their complexes were screened for their antibacterial activities against eight bacterial strains and the ligands and complexes have antibacterial effects. The most effective ones are [CuL2] against Proteus vulgaris, Serratia marcescens, Staphylococcus subtilis, [H2L1] against S. subtilis, and [H2L2] against S. subtilis.  相似文献   

13.
Treatment of [Fe(bipy)Cl4][bipy · H] (1) and [Fe(phen)Cl4][phen · H] (3) (where bipy is 2,2′-bipyridine and phen is 1,10-phenanthroline) with dimethyl sulfoxide in methanolic solution produced [Fe(bipy)Cl3(DMSO)] (2) and [Fe(phen)Cl3(DMSO)] (4) (where DMSO is dimethyl sulfoxide), respectively. The resulting complexes were characterized by elemental analysis, IR, UV–Vis and 1H NMR spectroscopies and by the X-ray diffraction method. These complexes are high spin with a spin multiplicity of 6.  相似文献   

14.
15.
Cobalt(II), nickel(II), and copper(II) complexes containing 5,12-di(4-bromophenyl)-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H2L1) and 5,12-diphenyl-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H2L2) have been synthesized. All complexes were characterized by elemental analysis, MALDI TOF-MS spectrometry, and electronic absorption spectroscopy. The crystal structures of two compounds, [Cu2(H2L1)Cl4]n and [NiL2], were determined by X-ray powder diffraction. In the polymeric [Cu2(H2L1)Cl4]n, the Cu2Cl4 units and H2L1 molecules are situated on inversion centers. Each Cu(II) has a distorted trigonal-bipyramidal coordination environment formed by N and O from H2L1 [Cu–N 2.340(14)?Å, Cu–O 1.952(11)?Å], two bridging chlorides [Cu–Cl 2.332(5), 2.279(5)?Å] and one terminal chloride [Cu–Cl 2.320(6)?Å]. In the [NiL2] complex, the Ni(II) situated on inversion center has a distorted square-planar coordination environment formed by four nitrogens from L2 [Ni–N 1.860(11), 1.900(11)?Å].  相似文献   

16.
The catalytic activity of a series of [Rh L-L chel]X complexes, in which we have varied the unsaturated ligand [L-L = cis, cis-cycloocta 1,5-diene(cod) or 2,5-norbornadiene(nbd) the nitrogen chelating ligand [chel = 2,2′-bipyridine(bipy), 2,2′-dipyridylamine(dipyam), 2,2′-bipyrazine (bipz), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bipy)] and the counter ion [X = PF6, ClO4, BPh4], has been examined in reactions with phyenylacetylene (PA). The catalytic behaviour of the [Rh(cod)Cl2],tmeda (tmeda = N,N,N′,N′tetramethylethylendiamine), [Rh(cod)Cl2],teda] (teda = triethylendiamine), of the dimer [Rh(cod)Cl]2, and the use of NaOH as cocatalyst in different reaction conditions was also examined. The influence of the ligands on the catalytic activity of these RhI complexes is discussed. 1H and 13C NMR spectra have shown that highly stereoregular polyphenylacetilene can be obtained. Conditions for homogeneous doping of PPA, to obtain materials whose conductivity varies over 10–11 magnitude orders, are proposed. The stability of the doped polymers is also discussed.  相似文献   

17.
Five zinc(II) complexes, [Zn(L1)2] (1), [Zn(L1)2(phen)H2O]·H2O (2), [Zn(L1)2(bipy)] (3), [Zn(L2)2] (4), and [Zn(L2)2(phen)] (5) (where L1?=?4-nitrophenylacetate, L2?=?phenylacetate, phen?=?1,10-phenanthroline and bipy?=?2,2′-bipyridine), have been synthesized and characterized by elemental analysis, FT-IR, and multinuclear NMR. Complexes 2, 3, and 4 have been confirmed by single-crystal X-ray diffraction. In 2 and 3, zinc is bonded monodentate to two carboxylates exhibiting distorted trigonal bipyramidal and tetrahedral geometries, respectively, whereas in 4, the carboxylates are bridging bidentate in distorted tetrahedral geometry. The complexes have been screened for electro- and biological activities, including DNA interaction and enzyme inhibition studies. The effect of concentration of 1–5 on the activity of enzyme, alkaline phosphatase, showed that an increase in concentration of complex decreased the activity of the enzyme. Electrochemical behavior of HL1, 2, and 3 was investigated by cyclic voltammetry and it was observed that ligand-centered electro-activity exhibits a proportionate change on complexation. The UV–visible spectroscopic and viscometric data indicate electrostatic and groove binding of the complexes with DNA. The binding constant and Gibb’s free energy values indicate the feasibility of the complex–DNA interaction and show potent biological activity of the complexes.  相似文献   

18.
Two manganese complexes, [Mn(L1)2(dibe)2](L1) (1) and [Mn(L2)2(dibe)2] (2) (where L1?=?2,2′-bipyridine (bipy), L2?=?1,10-phenanthroline (phen)), were synthesized by using a carboxylic acid ligand (dibe?=?2,2-dibenzylmalonate acid). The two complexes were characterized using IR, elemental analysis, and X-ray crystallography. Fluorescence analysis indicates that the two complexes can bind to HeLa cell DNA (HC-DNA), and gel electrophoresis assay demonstrates the ability of the complexes to cleave the HC-DNA. The two complexes exhibit cytotoxic specificity and significant cancer cell inhibitory rate. Furthermore, apoptotic tests demonstrate that these two complexes have apoptotic effects on HeLa cells.  相似文献   

19.
The synthesis of two ligands, L1 and L2, each containing two 2-oxy-1,10-phenanthroline moieties attached to the same phosphorus atom of a substituted cyclotriphosphazene ring via an oxy-bridge, but differing in substitution on the biphenyl capping groups, is described. The single-crystal X-ray structure of L1 · 2CH2Cl2 shows an ordered structure in the lattice with channels, containing dichloromethane molecules, running parallel to the a-axis. The reactions of L1 and L2 with [Cu(MeCN)4](PF6) afford the dimetallic copper(I) derivatives, [(CuL1)2] (PF6)2 · CH2Cl2 and [(CuL2)2](PF6)2. The single-crystal X-ray structure of the former complex shows that the L1 ligands of the cation [(CuL1)2]2+ act as a bridges coordinating to the two copper(I) centres in a helical fashion. The copper atoms have distorted tetrahedral geometries with the interligand dihedral angle being 85°. With copper(II) chloride and copper(II) perchlorate, the monomeric copper(II) complexes, [CuL1Cl]Cl · 2CH2Cl2, [CuL2Cl]Cl · CH2Cl2, [CuL1(OMe)]PF6 · 2H2O, [CuL2(OMe)]PF6 · 2H2O, [CuL1(OH2)](ClO4)2 and [CuL2(OH2)](ClO4)2 · H2O are obtained. The single-crystal X-ray structure of [CuL1Cl]Cl · 2CH2Cl2 shows the copper to be in a square-base pyramidal distorted trigonal-bipyramidal (SBPDTB) environment (τ = 0.57) with L1 acting as a κ4N donor, coordinating via the four nitrogen atoms of the two tethered 1,10-phenanthrolines. In CH3CN, this complex undergoes hydrolysis via the presence of adventitious water losing one oxyphenanthroline arm to form the centrosymmetric dimetallic species, [(CuL3Cl)2] · 4CH3CN · 3H2O (L3 = [N3P3(biph)2(ophen)O] where biph = 2,2′-dioxybiphenyl and O replaces an oxyphenanthroline and is attached to the phosphorus of the phosphazene ring). The two monomeric units, which are linked by bridging chlorine atoms, have a distorted square-based pyramidal geometry about the copper with the basal plane made by the ‘ON2Cl’ ligand set. Spectroscopic (mass spectral, electronic and ESR) and magnetic moment data for the complexes are discussed.  相似文献   

20.
Ruthenium(II) complexes containing two tetradentate ligands, 1,2-bis(o-aminophenylthio)ethane (L1) and 1,2-(oaminophenylthio)xylene (L2), have been prepared. The complexes, which are of the type Ru(L)Cl2 [L = L1 (1);/L2 (2)], [Ru(L)(PPh3)Cl]Cl [L = L1 (3); L2 (4)] and [Ru(L)(bpy)](PF6)2 [L = L1 (5);/L2 (6)], were characterised by elemental analysis, i.r., u.v.-vis. and n.m.r. spectroscopy and their electrochemical behaviour has been examined by cyclic voltammetry using a glassy carbon working electrode and an Ag/AgCl electrode as the reference electrode. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

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