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1.
A new monobasic bidentate ON donor Schiff base PS–LH2 (where PS–LH2 = polystyrene-anchored Schiff base obtained by condensation of chloromethylated polystyrene (containing 1.17 mmol of chlorine per gram of resin cross-linked with 2% divinylbenzene), 2-hydroxy-1-naphaldehyde and 4-aminosalicylic acid has been synthesized. PS–LH2 reacts with metal complexes to form polystyrene-anchored complexes: PS–LHM(CH3Coo) · DMF (where M = Cu, Zn, Cd, UO2), PS–LHZr(OH)2(CH3Coo) · 2DMF, PS–LHFeCl2 · 2DMF, PS–LHM′(CH3Coo) · 3DMF (where M′ = Mn and Ni) and PS–LHMoo2(acac), where acacH = acetylacetone. The polystyrene-anchored complexes have been characterized by elemental analysis, IR, ESR and magnetic susceptibility measurements. The per cent reaction conversion of PS–LH2 to polystyrene supported coordination compounds lies between 30–95. Shifts of the azomethine ν(C=N) and phenolic ν(C–O) stretches are indicative of ON donor behaviour of the polystyrene-anchored ligands. The complexes, PS–LHCu(CH3Coo) · DMF, PS–LHFecl2 · 2DMF, PS–LHMn(CH3Coo) · 3DMF and PS–LHNi(CH3Coo) · 3DMF are paramagnetic, while PS–LHZn(CH3Coo) · DMF, PS–LHCd(CH3COO) · DMF, PS–LHUo2(CH3Coo) · DMF, PS–LHZr(OH)2(CH3COO) · 2DMF and PS–LHMoO2(acac) are diamagnetic. The copper(II) complex exhibits a square planar structure, zinc(II) and cadmium(II) complexes have tetrahedral structures, nickel(II), manganese(II), iron(III), dioxomolybdenum(VI) and dioxouranium(VI) complexes have octahedral structure and zirconium(IV) complex is pentagonal bipyramidal.  相似文献   

2.
3.
A series of cation–anion complexes derived by 2,2′-dipyridylamine (Hdpa) and carboxylate ligands with formulas [Ni(Hdpa)2(CH3COO)]Cl(CH3OH) (1), [Co(Hdpa)2(CH3COO)]Cl(CH3OH) (2), [Ni(Hdpa)2(CH3CH2CH2COO)]Cl (3), [Co(Hdpa)2(CH3CH2CH2COO)]Cl (4), [Ni(Hdpa)2(C6H5COO)]Cl (5), and [Co(Hdpa)2(C6H5COO)]Cl (6), were synthesized and characterized by IR, elemental analysis, MS(ESI), TG analysis, UV-Vis, and fluorescence spectra. X-ray single crystal structural analysis showed that the coordination geometries of metal ions in these complexes are similar and they are cation–anion species. The hydrogen-bonding structures are 1-D chains through the N–H···Cl bonds. There are weak stacking interactions between pyridine rings in 14, while there are no stacking interactions in 5 and 6. We have investigated the transesterification of phenyl acetate with methanol catalyzed by 16 under mild conditions; 14 are homogeneous catalysts while 5 and 6 are heterogeneous catalysts due to their poor solubility in methanol. Cobalt complexes exhibit higher catalytic activities than corresponding nickel complexes. Complex 4 is the best catalyst of these six complexes.  相似文献   

4.
Two multinuclear Co(II) complexes, [{Co(L)(i-PrOH)}2Co(H2O)]?2CH3CN (1) and [{Co(L)(μ-OAc)Co(MeOH)2}2]?2CH3COCH3 (2), have been synthesized with a new asymmetric Salamo-type ligand (H3L = 6-hydroxy-6′-ethoxy-2,2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol). The Co(II) complexes were obtained by different solvents, and the structures are completely different. In the Co(II) complex 1, the ratio of the ligand H3L to Co(II) atom is 2 : 3 and the Co(II) ions are all five-coordinate with trigonal bipyramidal geometries. In the Co(II) complex 2, the ratio of the ligand H3L to Co(II) atom is 2 : 4. Two central Co(II) ions are six coordinate with distorted octahedral geometries and two terminal Co(II) ions are five coordinate with distorted trigonal bipyramidal geometries. Self-assembling of an infinite 1-D supramolecular chain is formed by C–H?π interactions in 1. Interestingly, an infinite 2-D-layer plane structure is formed by the self-assembling array of 2 linked by C–H?π interactions. 1 and 2 exhibit blue emissions with the maximum emission wavelengths λmax? = 403 and 395 nm when excited at 330 nm.  相似文献   

5.
Coordination polymers were obtained by the reaction of metal acetates, M(CH3COO)2·xH2O {where M = Mn(II), Co(II), Ni(II) and Cu(II)} with AFP ligand (AFP = 5,5'-(piperazine-1,4-diylbis(methylene))bis(2-aminobenzoic acid). The AFP ligand was prepared by the one-pot, two-step reaction of formaldehyde, 2-aminobenzoic acid, and piperazine. Structural and spectroscopic properties have been studied by elemental, spectral (FT-IR, 1H NMR, 13C NMR, and UV–vis), and thermogravimetric analysis. UV–vis spectra and magnetic moment values indicate that Mn(II), Co(II), and Ni(II) polymer–metal complexes are octahedral, while Cu(II) and Zn(II) polymer–metal complexes are distorted octahedral and tetrahedral, respectively. The analytical data confirmed that the coordination polymers of Mn(II), Co(II), Ni(II), and Cu(II) are coordinated with two water molecules, which are further supported by infrared spectra and thermogravimetric analysis data. The prepared polymer–metal complexes showed good antibacterial activities against all tested microorganisms; however, the AFP ligand was also found to be effective, but relatively less than their polymer–metal complexes. Along with antibacterial activity, all the polymer–metal complexes exhibit significant antifungal activity against most of the tested fungal strains. The results of antimicrobial activity reveals that the AFP–Cu(II) showed the highest antibacterial and antifungal activity than other polymer–metal complexes.  相似文献   

6.
Cobalt(II) complexes of N-methyl phenyl, 1-phenylpiperazyl, and morpholinyl dithiocarbamates have been synthesized and characterized by UV–Visible, FTIR, 1H-, 13C-NMR, and mass spectrometry. The spectroscopic data indicated that two ligands coordinated in bidentate chelating to the metal ion to form four-coordinate cobalt(II) complexes (13), which was confirmed by mass analysis (TOF MS ES+) of the complexes with m/z [M]+ = 450.98, 382.94, and 382.94 for 1, 2, and 3, respectively. Single crystal analysis of 2A and 3A show centrosymmetric mononuclear cobalt(III) bonded to three dithiocarbamate ligands forming a distorted octahedral geometry, indicating the cobalt(II) undergoes aerial oxidation to cobalt(III) during recrystallization. In addition, 2A crystallized with one solvated molecule of toluene. The redox behaviors of the complexes were studied by cyclic and square wave voltammetry in dichloromethane; the result revealed a metal centered redox process consisting of a one-electron quasi-reversible process assigned to Co(III)/Co(IV) oxidation and a corresponding Co(IV)/Co(III) reduction. Randles–Sevcik plots (anodic peak current versus the square root of the scan rate (Ip,a versus ν1/2)) for the redox couples revealed diffusion-controlled behavior.  相似文献   

7.
Self-assemblies of the flexible ferrocenyl block 2-chloro-4-ferrocenylbenzoate with Cd2+ cations in the presence of N-containing auxiliary ligand result in two coordination complexes, namely, &{[Cd(η2 -OOCClH3C6Fc)2(Mbbz)(CH3OH)] · (H2O)0.5} n (I) and [Cd(η2 -OOCClH3C6Fc)2(Bbbm)] n (II) {Fc = (η5- C5H4)Fe(η5-C5H4), Mbbz = 1,1'-methyl benzimidazole, Bbbm = 1,4-bis(benzimidazol-1-ylmethyl)-benzene}. Their structure has been determined by single-crystal X-ray diffraction analyses (CIF files nos. 1529095 (I), 1529096 (II)) and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Crystallographic characterization shows that both I and II are 1D chain structures. Notably, various C–H···π interactions and C–H···Cl interactions are discovered in I and II, and they have significant contributions to self-assembly, which extend 1D complex to infinite 3D supramolecular networks. Moreover, the electrochemical studies of I and II in DMF solution display irreversible redox waves and indicate that the half-wave potentials of the ferrocenyl moieties in I and II are shifted to positive potential compared with that of free 2-chloro-4-ferrocenylbenzoate.  相似文献   

8.

The new complexes of 2-[(2-oxo-1,2-dihydroindol-3-ylidene)amino]butanoic acid, LH (where L = C12H11N2O3), with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) of general formulae MLCl·nH2O, for Co(II), Ni(II) and Cu(II), and ML2·H2O for Mn(II) and Zn(II), where n = 1, 2 depending on M(II) ions, are synthesized. The complexes crystallize in a monoclinic system, and upon heating in the air (293–1173 K) decompose in three steps forming eventually the corresponding oxides of the metals(II). In the course of this process the organic ligand decomposes releasing the molecules of H2O, CO2, NH3, CO, hydrocarbons, and additionally HCl for Co(II), Ni(II) and Cu(II) complexes. Magnetic moments of compounds are determined in the ranges of 76–303 and 2–300 K. All analyzed compounds, except that of Zn(II), demonstrate the paramagnetic properties with the ferro- and antiferromagnetic interactions between molecular centres.

  相似文献   

9.
Similar to the antibiotic mixing strategies, which depend on reducing the worth of diffusion of the resistant bacteria to new host, in this contribution, we explicit new mixed-ligand complexes of the type [M(SMZ)2(BZM)] (M = Co(II), Ni(II) and Cu(II)) based on two drugs: sulfamethazine (SMZ) and bromazepam (BZM). The novelty aspect of the present work relies on combining two drugs in a single molecule via the synthesis of the ternary complexes. The ternary complexes were characterized by spectroscopic and analytical tools with the aid of the quantum chemical calculations. Copper(II) complex has the highest DNA intrinsic binding constant (2.20 × 105 M−1), induces extensively DNA cleavage compared to the other complexes, and exhibits the highest cytotoxicity (IC50 = 0.67 μM) against human liver cancer cell line (HepG2). Exciting, Cu(II) compound exhibits no toxicity to the nonmalignant human foetal lung fibroblast (WI-38). Alternatively, the low cytotoxicity of the Co(II) complex correlates well with the high affinity of the compound to human serum albumin (Kb = 4.58 × 105) compared to 1.93 × 105 and 2.14 × 105 M−1 for Ni (II) and Cu (II) complexes, respectively.  相似文献   

10.
Complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with diacetyl benzaldehyde oxalic acid dihydrazone (dbodh), CH3COC(CH3)=NNHCOCONHN=CHC6H5 and diacetyl benzaldehyde malonic acid dihydrazone (dbmdh), CH3COC(CH3)=NNHCOCH2CONHN=CHC6H5 of general composition [M(dbodh)Cl]Cl and [M(dbmdh)Cl]Cl were synthesized and characterized by microanalyses, molar conductance, magnetic susceptibility, UV–Vis, ESR and IR spectra and X-ray diffraction studies. The complexes are 1 : 1 electrolytes in DMF and are insoluble in water and common organic solvents. The dbodh and dbmdh are neutral tridentate ligands in most complexes and coordinate via one >C=O and two >C=N–groups. In Cu(II) complexes the ligands are pentadentate coordinating through three >C=O and two >C=N–groups. The magnetic moment values and UV–Vis spectra suggest square-planar geometry for Co(II) and Ni(II) complexes and distorted octahedron for both Cu(II) complexes. The ESR spectra of Cu(II) complexes show well-defined copper hyperfine lines in DMSO solution at 120 K and exhibit d x 2 ?y 2 as the ground state. The X-ray diffraction parameters for [Ni(dbodh)Cl]Cl and [Co(dbmdh)Cl]Cl correspond to a tetragonal crystal lattice. The complexes show significant antifungal activity against Alternaria sp., Curvularia sp. and Colletotrichum sp. and fair antibacterial activity against Bacillus subtilis and Pseudomonas fluorescence.  相似文献   

11.
Three multinuclear complexes, [Co(L)(OAc)Co(CH3CH2OH)2]·H2O, [Zn(L)(OAc)Zn(CH3OH)], and [{Cd(L)(OAc)Cd(CH3OH)}2], containing a single-armed salamo-type bisoxime H3L have been synthesized and characterized structurally. The Co(II) complex forms a dimeric unit by intermolecular hydrogen bond interactions of neighboring dimeric molecules. The Zn(II) complex also forms a dimeric unit by intermolecular hydrogen bond interactions. Interesting features of the crystal structure include O?O short contacts. Meanwhile, self-assembling infinite 1-D, 2-D, and 3-D supramolecular structures are formed by intermolecular hydrogen bond and C–H?π interactions. The Cd(II) complex forms an infinite 2-D supramolecular structure by intermolecular hydrogen bond interactions. The photophysical properties of the Co(II), Zn(II), and Cd(II) complexes have also been discussed.  相似文献   

12.
A Schiff base ligand (HL), 2,4-dimethoxy-N-(5-chloro-2-hydroxybenzylidene)-benzenamine, derived from 5-chloro-2-hydroxybenzaldehyde and 2,4-dimethoxyaniline, and its metal complexes [Co(L)2]·CH3OH (1), [Ni(L)2] (2), [Cu(L)2] (3) have been synthesized. The compounds were characterized by analytical and spectroscopic methods. In addition, the structures of the Schiff base HL and its Co(II) complex were determined by single-crystal X-ray analysis. The Co(II) center is six-coordinate, being coordinated to two imine nitrogen, two phenolate oxygen and two methoxy oxygen atoms of two crystallographically independent Schiff base ligands. Luminescence properties of HL and its complexes were investigated both in solution and in the solid state.  相似文献   

13.
A new asymmetric Salamo‐based ligand H2L was synthesized using 3‐tertbutyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H2L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}2], and [{Ni(L)(CH3COO)(CH3CH2OH)}2Ni] with the ligand H2L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H2L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.  相似文献   

14.
Six coordination compounds constructed by two structurally related flexible nitrogen-containing polycarboxylate ligands 2,2′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)dibenzoic acid (H2L1) and 5,5′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)diisophthalic acid (H4L2) have been synthesized: [Ni(H2O)6]?·?L1?·?(C2H5OH)0.5?·?H2O (1), [Co(L1)(L3)]?·?CH3OH (2), [Ni(L1)(L3)]?·?CH3OH (3), [Zn(L1)(L3)]?·?CH3OH (4), [Cd(L1)(L3)]?·?CH3OH (5), and [Zn(L2)0.5(phen)]?·?C2H5OH (6), where L3?=?3,4?:?9,10?:?17,18?:?23,24-tetrabenzo-1,12,15,26-tetraaza-5,8,19,22-tetraoxacyclooctacosan and phen?=?1,10-phenanthroline. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 displays a discrete structure, which is further linked by hydrogen bonds to form a 2-D supramolecular layer. Compounds 25 display similar structures. These compounds possess 1-D meso-chain structures linked by L1 and metals. The C–H?···?π interactions from neighboring chains extend the chains in different directions, giving a 3-D plywood network. Compound 6 possesses 2-D layers, which are further linked by hydrogen-bonding interactions to generate a 3-D supramolecular architecture.  相似文献   

15.
The simultaneous TG/DTG–DTA technique was used for three new cobalt(II) complexes with dipyridylamine (dpamH) and the anion of a 2-hydroxyphenone ligand (phenone), with the general formula [Co(dpamH)2(phenone)]Br, in order to determine their thermal degradation in static air and dynamic nitrogen atmospheres, which was found to be a multi-step decomposition related to the release of the ligand molecules. The complexes were characterized by elemental analyses, FT-IR and UV–Vis spectroscopy, magnetic and conductivity measurements. All structures were determined by X-ray crystallography revealing octahedral coordination of cobalt(II) and monomeric nature of the compounds, [Co(dpamH)2(2-OH-acetophenone)]Br (1), [Co(dpamH)2(2-OH-propiophenone)]Br (2) and [Co(dpamH)2(2-OH, 5-CH3-acetophenone)]Br·EtOH (3). The variable temperature (76–303 K) magnetic susceptibility measurements showed a paramagnetic nature of the complexes, in accordance with their molecular structure.  相似文献   

16.
New N2O2 donor type Schiff bases have been designed and synthesized by condensing acetylaceto-4-aminoantipyrine/acetoacetanilido-4-aminoantipyrine with 2-amino benzoic acid in ethanol. Solid metal complexes of the Schiff bases with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, FAB Mass, IR, UV-Vis., 1H NMR, and ESR spectral studies. The data show that the complexes have a composition of the ML type. The UV-Vis., magnetic susceptibility, and ESR spectral data of the complexes suggest a square planar geometry around the central metal ion, except for VO(IV) complexes, which have square-pyramidal geometry. The redox behavior of copper and vanadyl complexes has been studied by cyclic voltammetry. The nuclease activity of the above metal complexes shows that the complexes cleave DNA through redox chemistry. In the presence of H2O2, all the complexes are capable of cleaving calf thymus DNA plasmids, in order to compare the cleavage efficiency of all metal complexes in the two different ligand environments. In this assay, Cu(II), Ni(II), Co(II), and Zn(II) exhibit more cleavage efficiency than other metal ions. This article was submitted by the authors in English.  相似文献   

17.
Two novel oxamido-bridged macrocyclic complexes, [LCu(CH3OH)Co(phen)2](ClO4)2·CH3OH (1) and [LCu(CH3OH) Cu(phen)2](ClO4)2·CH3OH (2) (where H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,10,12-trimethyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene, phen = 1,10-phenanthroline), have been prepared by stepwise synthesis and characterized. In both complexes, each Cu(II) atom from the precursor ligand CuL is connected to a Co(II) (or Cu(II)) atom via the exo–cis oxygen atoms, resulting in a binuclear subunit. Magnetic susceptibility measurements in the 2–300 K temperature range have been taken for the two complexes.  相似文献   

18.
Phosphoraneiminato‐Acetato Complexes of Cobalt and Cadmium with M4N4 Heterocubane Structure The phosphoraneiminato‐acetato complexes [M(NPEt3)(O2C–CH3)]4 with M = Co and Cd are formed from the anhydrous metal(II) acetates with excess Me3SiNPEt3 at 180 °C. By crystallization from diethyl ether blue, moisture sensitive single crystals of [Co(NPEt3) · (O2C–CH3)]4 can be obtained, while colourless single crystals of [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2 originate from dichloromethane solution. In vacuo the intercalary CH2Cl2 is released. The complexes are characterized by their IR spectra and by crystal structure analyses. In both complexes the metal atoms are associated via μ3–N bridges of the (NPEt3) groups to form heterocubanes. In the cobalt complex the acetato ligands are bonded in a semichelate fashion with a short Co–O and a long Co–O bond each (Co–O distances in average 199.5 and 257.4 pm). In the cadmium complex the acetato groups form almost symmetrical chelates (Cd–O distances in average 232.1 and 237.8 pm); this leads to a distorted trigonal‐bipyramidal arrangement at the cadmium atoms. [Co(NPEt3)(O2C–CH3)]4: Space group P 1, Z = 4, lattice dimensions at –60 °C: a = 1110.1(2), b = 2051.3(5), c = 2169.5(4) pm, α = 100.03(2)°, β = 103.404(15)°, γ = 97.63(2)°, R = 0.0480. [Cd(NPEt3)(O2C–CH3)]4 · 2 CH2Cl2: Space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1550.2(1), b = 2101.1(1), c = 1706.1(1) pm, β = 91.09(1)°, R = 0.0311.  相似文献   

19.
Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L1)2]?·?H2O (1), [Ni(L1)2]?·?H2O (2), [Ni(L2)2] (3), and [Co(L3)2]?·?H2O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL1), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL2), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL3) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL1 and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.  相似文献   

20.
The electrochemical behavior of iron diimine complexes, (H3C?N=C(R)?C(R′)=N?CH3)3Fe(II) (R, R′=H,H;H, CH3; CH3, CH3), and (C5H4N?C(R1)=N(R2))3Fe(II) (R1, R2=H, CH3; CH3, CH3) on a platinum working electrode in acetonitrile is described, and compared to that of the parent aromatic complex, tris-(2,2′-bipyridine)Fe(II). One-electron reversible oxidations were found for all the compounds studied. The electrochemical reductions show 2–3 reduction waves in the potential range studied. Only for the complexes of mixed diimine ligands or 2,2′-bipyridine, a pre-adsorption wave is also observed. It is possible to stabilize low valence states with all ligands studied. A formal iron(I) state is described for the first time for all aliphatic diimine complexes, thus showing that the acceptor properties of the diimine complexes do not depend on the presence of the aromatic rings, but on the iron-diimine chromophore.  相似文献   

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