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1.
A Schiff base ligand containing thiocarbamide group of 4-phenyl-1-(4-methoxyl-1-phenylethylidene)thiosemicarbazide (HL) and its three mononuclear metal complexes of ZnL2 (1), NiL2 (2), and CuL2 (3) have been synthesized. Elemental analysis, IR, and X-ray single crystal diffraction characterizations for the ligand and the three complexes have been carried out. In the three complexes, the central metallic ions of Zn2+, Ni2+, and Cu2+ coordinate with two deprotonated ligands of L, respectively. In 1, Zn2+ ion adopts a distorted tetrahedral geometry, while in 2 and 3, both the Ni2+ and Cu2+ ions possess distorted square planar configurations. For the four compounds, UV–Vis spectra have been measured and DFT calculations at B3LYP/LANL2DZ level of theory prove that the electronic spectra of HL and 1 are corresponding with electronic transitions of n → π* and π → π* in the ligand itself and the electronic spectra of 2 and 3 are attributed to intraligand electronic transitions as well as dd electronic transitions. Electrochemical investigations reveal that the different metal–ligand interactions have changed the peak shapes and peak locations, which are corresponding with the DFT-B3LYP/LANL2DZ calculational results. Fluorescence spectra measurements indicate that the ligand emits purple fluorescence and the complex 1 emits stronger blue fluorescence, while the complexes 2 and 3 quench fluorescence. The thermal analyses result show that the three complexes undergo two similar decomposition processes because of their similar geometric configurations.  相似文献   

2.
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   

3.
An N3O Schiff base (L), 1?:?1 condensate of benzil monohydrazone and 4-pyridine carboxaldehyde, and its Zn(II), Cd(II), and Ag(I) complexes were synthesized and characterized by elemental analyses and various spectroscopic techniques. The crystal structures of [ZnL2Br2] (1), [CdL2I2]·CH2Cl2, (2)·CH2Cl2, and [Ag(L)2]ClO4 (3) have been determined using X-ray crystallography. The Zn(II) and Cd(II) complexes show a tetrahedral configuration whereas in the asymmetric unit of 3, two independent coordination units of Ag(I) are present. Carbonyl–silver interaction, weak C–H?O interaction, and also π–π interaction are present in 3 in the solid state. The synthesized complexes have antibacterial activity against Klebsiella pneumoniae 114, Escherichia coli K88, Salmonella typhi ATCC 34, Bacillus subtilis UC564, and Staphylococcus aureus ATCC25923. The results showed that in some cases the antibacterial activities of the complexes were comparable to standard antibiotics Tetracycline and Streptomycin. The antifungal activities of the complexes were also studied for Aspergillus niger, Aspergillus oryzae, Penicillium notatum, and Saccharomyces cerevisiae. MIC values of 1, 2·CH2Cl2, and 3 are less than the Nystatin standard.  相似文献   

4.
Complexes represented by the general formula [MCl2L2] (M(II)=Zn, Mn, Co) and complexes of [Cu3Cl6L4] and CuSO4L2·4H2O, CoSO4L2·3H2O, [ZnSO4L3] where L stands for 3-amino-5-methylpyrazole were prepared. The complexes were characterized by elemental analysis, FT-IR spectroscopy, thermal (TG, DTG, DSC and EGA) methods and molar conductivity measurements. Except for the Zn-complexes, the magnetic susceptibilities were also determined. Thermal decomposition of the sulphato complexes of copper(II) and cobalt(II) and the chloro complexes of cobalt(II) and manganese(II) resulted in well-defined intermediates. On the basis of the IR spectra and elemental analysis data of the intermediates a decomposition scheme is proposed. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

5.
This article presents a combined experimental and computational study of the complexes [Cu(dafone)2(SCN)2] (1), [Ni(dafone)2(SCN)2] (2) and [Hg(dafone)(SCN)2] (3), where dafone stands for 4,5-diazafluoren-9-one. The compounds have been studied by IR, UV–Vis spectroscopy, and single crystal X-ray diffraction. The electronic structures of these complexes have been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1, 2, and 3 have been calculated with the time-dependent DFT method, and their UV–Vis spectra have been discussed on this basis.  相似文献   

6.
Four new supramolecular compounds, (2-mimH)[Ca(pydcH)3][Ca(pydcH2)(pydc)(H2O)2]·4H2O (1), (1-mimH)2[Zr(pydc)3] (2), (2-mimH)2[Cd(pydc)2]·8H2O (3), and (2-mimH)2[Hg(pydc)2]·8H2O (4) [where pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), 1-mim = 1-methylimidazole, and 2-mim = 2-methylimidazole], have been synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV–vis, 1H NMR, and 13C NMR), thermal (TG/DTG/DTA) analysis as well as single-crystal X-ray diffraction. All four compounds are proton-transfer salts of the methylimidazolium cations and metal complex anions that crystallized from a solution of pyridine-2,6-dicarboxylic acid, methylimidazole, metal nitrates or chlorides as starting materials. The coordinating dicarboxylic acid is deprotonated at the carboxyl group and methylimidazole is protonated to balance the charge. In the crystal structures of 14, hydrogen bonding and ππ stacking play important roles. Water clusters are formed in 1, 3, and 4. The equilibrium constants of dipicolinic acid (pydc) and methylimidazole derivatives (1-mim and 2-mim), pydc-2-mim, pydc-1-mim proton-transfer systems as well as those of their complexes were investigated by a potentiometric pH titration method. The stoichiometries of most of the complex species in solution were very similar to the cited crystalline metal ion complexes.  相似文献   

7.
New complexes, [Fe(L)Cl], [Ni(L)], and [Zn(L)C2H5OH] (1–3), were synthesized by template reaction of 2-hydroxy-acetophenone-S-methyl-thiosemicarbazone with 2-hydroxy-benzaldehyde. The compounds were characterized by elemental analysis, magnetic measurements, FT-IR, 1H NMR, UV–visible, and ESI–MS spectra. In these complexes, the ligand is coordinated to the metal ion as dinegatively charged tetradentate chelating agents via the N2O2 donor set. The iron(III) and zinc(II) complexes exhibit square pyramidal geometry whereas the nickel(II) complex has a square planar geometry. The crystal structure of 1, determined by X-ray diffraction method, indicates that 1 crystallizes in the monoclinic space group P21/c with Z = 4. Thermal decompositions of the compounds have been investigated using TGA in air.  相似文献   

8.
The [Co(HOr)(H2O)2(im)2] (1), [Ni(HOr)(H2O)2(im)2] (2), [Zn(H2O)2(im)4](H2Or)2 (3) and [Cd(HOr)(H2O)(im)3] (4) complexes (H3Or: orotic acid, im: imidazole) were synthesized and characterized by elemental analysis, magnetic and conductance measurements, UV-vis and IR spectra. The thermal behaviour of the complexes was also studied by simultaneous thermal analysis techniques (TG, DTG and DTA). The orotate ligand (HOr2−) coordinated to the Co(II), Ni(II) and Cd(II) ions are chelated to the deprotonated pyrimidine nitrogen (N(3)) and the carboxylate oxygen, while do not coordinate to the Zn(II) ion is present as a counter-ion (H2Or). The first thermal decomposition process of all the complexes is endothermic deaquation. This stage is followed by partially (or completely) decomposition of the imidazole and orotate ligands. In the later stage, the remained organic residue exothermically burns. On the basis of the first DTGmax, the thermal stability of the complexes follows order: 2, 176°C>1, 162°C>4, 155°C>3, 117°C in static air atmosphere. The final decomposition products which identified by IR spectroscopy were the corresponding metal oxides.  相似文献   

9.
The phosphonium salts [Ph2P(CH2)nPPh2CH2C(O)C6H4-m-OMe]Br (n = 1 (S1) and n = 2 (S2)) were synthesized in the reaction of bis(diphenylphosphino)methane (dppm) and bis(diphenylphosphino)ethane (dppe) with 2-bromo-3?-methoxy acetophenone, respectively. Further treatment with NEt3 gave the phosphorus ylides Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe (n = 1 (Y1) and n = 2 (Y2)). These ligands were treated with [MCl2(cod)] (M = Pd or Pt; cod = 1,5-cyclooctadiene) to give the P, C-chelated complexes, [MCl2(Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-OMe)] (n = 1, M = Pd (3), Pt (4), and n = 2, M = Pd (5), Pt (6)). These compounds were characterized by elemental analysis, spectroscopic methods, UV–visible, and fluorescence emission spectra. Further, the structures of complexes 3 and 6 were characterized crystallographically. The palladium complexes 3 and 5 proved to be excellent catalysts for the Suzuki reactions of various aryl chlorides. Also, a theoretical study on the structure of complexes 3–6 has been investigated at the BP86/def2-SVP level of theory. The strength and nature of donor?acceptor bonds between the phosphorus ylides (L) and MCl2 fragment in the [LMCl2] (M = Pd, Pt, L = Y1, Y2) were studied by NBO and energy decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV).  相似文献   

10.
Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL1), N-(3-hydroxybenzyl)-alanine acid (HL2), N-(3-hydroxybenzyl)-phenylalanine acid (HL3), and N-(3-hydroxybenzyl)-leucine acid (HL4), were synthesized and characterized on the basis of 1H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L1)2]·2H2O (1), [Cu(L2)2(H2O)] (2), [Cu(L3)2(CH3OH)] (3), and [Cu(L4)2(H2O)]·H2O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?106?M?1, 4.32?×?105?M?1, 5.00?×?105?M?1, and 5.70?×?104?M?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.  相似文献   

11.
Abstract

Five coordination complexes with Mn2+ (1), Co2+ (2), Ni2+ (3), Cu2+ (4), and Zn2+ (5) containing acesulfame (ace) and N,N-diethylnicotinamide (dena) ligands were synthesized and structural binding properties investigated. Four compounds (1, 2, 4, and 5) were examined with single crystal X-ray diffraction methods. The structures containing Mn(II), Co(II), and Zn(II) were iso-structural. Six-coordination of metal cations were completed with two moles dena and four aqua ligands. The dena ligands were coordinated via pyridine nitrogen as neutral-monodentate. Charge stabilities of the complexes are complemented by two moles monoanionic ace ligands, located outside of the coordination unit. In the Cu(II) complex, the coordination is completed by acidic nitrogen and carbonyl oxygen atoms of two ace ligands and pyridine nitrogen of two moles dena ligands. The coordination to Cu(II) for ace ligands was monoanionic-bidentate. All metal cations in the structure are distorted octahedral. Thermal decomposition of complexes begins with removal of the aqua molecules from the structures and is completed by combustion of organic ligands. The final decomposition products of all structures have been identified as corresponding metal oxides. Some biological applications (anti-fungal/anti-bacterial) were studied using 15.  相似文献   

12.
Coordination behavior of 4,5,6,7-tetrahydro-1H-indazole (H-Ind) with Cu(II), Co(II), and Ag(I) was studied. The ligand affords complexes bearing different geometries depending upon the metal and anion present in the starting salts. Five compounds with different structural perspectives, trans-[CuCl2(H-Ind)4] (1), trans-[CuBr2(H-Ind)4] (2), trans-[Cu(CH3COO)2(H-Ind)2] (3), trans-[CoCl2(H-Ind)4] (4), and [Ag(H-Ind)2]NO3 (5), were obtained. The ligand adopts tetrahydro-1H-indazole isomeric form in Cu(II) and Co(II) complexes and with Ag(I) ion the same ligand adopts tetrahydro-2H-indazole form. In the case of sterically demanding acetate counter ion in contrast to Cl or Br, the Cu(II) ion accepts two equivalents of the ligand and four-coordinated square planar complex was obtained. With AgNO3, the expected complex was obtained. The yield of reactions was >80% and all complexes were obtained as crystalline material from the reaction mixtures. Their structures were determined by X-ray diffraction and all complexes were tested for antibacterial (Enterobacter sakazkii, Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniea), antifungal (Aspergillus flavus, Aspergillus fumegatus, Aspergillus nigar, Fusarium oxysporium), and antioxidant (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) and 2,2-diphenyl-1-picrylhydrazyl (DPPH)) activities. The same were also tested as inhibitors against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) .  相似文献   

13.
Nickel(II) and cobalt(II) complexes with optically active diaminodioxime (H2L, the derivative of 3-carene) of the compositions [Ni(H2L)NO3]NO3 (I), Ni(H2L)Cl2 (II), [Ni(HL)]ClO4 · H2O (III), and Co(H2L)Cl2 (IV), were synthesized. According to X-ray diffraction data, the structures of the paramagnetic compound I and diamagnetic complex III are ionic. In the cation of I, the distorted NiN4O2 octahedron is formed by the N atoms of the tetradentate cyclic ligand (H2L molecule) and by the O atoms of NO3 –; anion functioning as bidentate cyclic ligands. In the cation of III, the NiN4 coordination unit is a distorted square formed upon coordination of the tetradentate cyclic ligand, HL–; anion. The data of magnetochemistry and UV-Vis, IR, and Raman spectroscopy suggest that paramagnetic complexes II and IV contain a distorted octahedral polyhedron MCl2N4 (M = Ni, Co).  相似文献   

14.
New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co3L6(H2O)5(C2H5OH)](NO3)6 · 2H2O · C2H5OH (I), [Ni3L6(H2O)6](NO3)6 · 2H2O (II), and [M3L6(H2O)6](ClO4)6 · nH2O (M = Co2+, n = 2 (III); Ni2+, n = 2 (IV); Cu2+, n = 0 (V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy, and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound I, [Co3L6(H2O)6](ClO4)6 · 8C2H5OH (IIIa), and [Ni3L6(H2O)6](ClO4)6 · 8C2H5OH (IVa) are determined.  相似文献   

15.
Transition metal complexes [Fe(HL)2]Cl3 ? 1.5H2O (1), [Co(L)2] ? ClO4 ? H2O (2), Ni(HL)2(ClO4)2 ? 2H2O (3), Zn(HL)L ? BF4 ? 2H2O (4), and Cd(HL)2(ClO4)2 ? 2H2O (5), where HL = C7H9N5S, 2-acetylpyrazine thiosemicarbazone, have been synthesized. Complex 2 was characterized by elemental analysis, infrared spectra, mass spectra, and single-crystal X-ray diffraction. Preliminary in vitro screening showed that 1, 4, and 5 exhibit higher antitumor activity than 2 and 3 against K562 leucocythemia cancer cell line.  相似文献   

16.
New bi- and trihomonuclear Mn(II), Co(II), Ni(II), and Zn(II) complexes with sulfa-guanidine Schiff bases have been synthesized for potential chemotherapeutic use. The complexes are characterized using elemental and thermal (TGA) analyses, mass spectra (MS), molar conductance, IR, 1H-NMR, UV-Vis, and electron spin resonance (ESR) spectra as well as magnetic moment measurements. The low molar conductance values denote non-electrolytes. The thermal behavior of these chelates shows that the hydrated complexes lose water of hydration in the first step followed by loss of coordinated water followed immediately by decomposition of the anions and ligands in subsequent steps. IR and 1H-NMR data reveal that ligands are coordinated to the metal ions by two or three bidentate centers via the enol form of the carbonyl C=O group, enolic sulfonamide S(O)OH, and the nitrogen of azomethine. The UV-Vis and ESR spectra as well as magnetic moment data reveal that formation of octahedral [Mn2L1(AcO)2(H2O)6] (1), [Co2(L1)2(H2O)8] (2), [Ni2L1(AcO)2(H2O)6] (3), [Mn3L2(AcO)3(H2O)9] (5), [Co3L2(AcO)3(H2O)9] · 4H2O (6), [Ni3L2(AcO)3(H2O)9] · 7H2O (7), [Mn3L3(AcO)3(H2O)6] (9), [Co2(HL3)2(H2O)8] · 4H2O (10), [Ni3L3(AcO)3(H2O)9] (11), [Mn3L4(AcO)3(H2O)9] · H2O (13), [Co2(HL4)2(H2O)8] · 5H2O (14), and [Ni3L4(AcO)3(H2O)9] (15) while [Zn2L1(AcO)2(H2O)2] (4), [Zn3L2(AcO)3(H2O)3] · 2H2O (8), [Zn3L3(AcO)3(H2O)3] · 3H2O (12), and [Zn3L4(AcO)3(H2O)3] · 2H2O (16) are tetrahedral. The electron spray ionization (ESI) MS of the complexes showed isotope ion peaks of [M]+ and fragments supporting the formulation.  相似文献   

17.
Three new reduced amino-acid Schiff-base complexes, [Zn(HL)2] · H2O (1), [Ni(HL)2] · H2O (2), and [Cd(HL)2] · H2O (3), where H2L is a reduced Schiff base derived from condensation of N-(2-hydroxybenzaldehyde) and L-histidine, have been synthesized and characterized by elemental analysis, UV-Vis absorption spectra and single crystal X-ray diffraction. Complexes 13 are isostructural. All metal centers are six-coordinate with O2N4 donor sets in slightly distorted octahedra. Unlike its Schiff-base counterpart, the deprotonated monoanionic ligand HL? has a more flexible backbone and two HL? are tridentate to one metal. Moreover, the binding interactions of these complexes with calf thymus DNA (CT-DNA) have been investigated by UV-Vis spectra and fluorescence quenching, which show that the complexes bind in an intercalative mode.  相似文献   

18.
Three new complexes: [Cd(btaa)(bipy)(CH3COO) · H2O] n (1), [Ni(btaa)2(H2O)4 · 6H2O] n (2), and [Mn(btaa)2(H2O)2] n (3) (bipy = 2,2′-bipyridine, Hbtaa = 1H-benzotriazole-1-acetic acid) were prepared and characterized by IR, elemental analyses, thermogravimetric analyses, and single-crystal X-ray analyses. In 1, cadmium ions are linked by btaa ligands into 1-D linear chains; the chains are extended into layers through C–H ··· O hydrogen bonds and π–π stacking interactions. Complex 2 is a mononuclear structure, extended to a 3-D network through multiple intermolecular hydrogen bonds. In 3, manganese is bridged by carboxylate groups of btaa in the syn–skew bidentate mode in two directions to form a 2-D grid-like framework with a (4, 4) topology. The solid-state fluorescence spectrum of 1 shows that the excitation peak is at 355 nm while the maximum emission peak is at 424 nm.  相似文献   

19.
Three new mononuclear Schiff-base complexes, namely [Mn(L)Cl] (1), [Ni(L)] (2), and [Cu(L)] (3), where L?=?anion of [N,N′-bis(2-hydroxybenzophenylidene)]propane-1,2-diamine, have been synthesized by reacting equimolar amounts of the respective metal chloride and the tetradentate Schiff base, H2L, in methanol. The complexes have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction, and other physicochemical studies. Structural studies reveal that 1 adopts a distorted square-pyramidal geometry whereas 2 and 3 are isotypic with distorted square-planar geometries. The antibacterial activities of 13 along with their Schiff base have been tested against some Gram(+) and Gram(?) bacteria.  相似文献   

20.
Salicylaldehyde 2-phenylquinoline-4-carboylhydrazone (H2L), and its novel copper(II), cobalt(II), and nickel(II) complexes MHL · Cl · nH2O [M=Cu n = 3 (1), M=Co n = 2 (2), M=Ni n = 3.5 (3)] have been synthesized and characterized by elemental analysis, molar conductivity, spectroscopic, and thermal analysis. The interaction of these complexes with calf thymus DNA was investigated by UV absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and viscosity measurements. The results suggest that these complexes bind to DNA via an intercalation binding mode and their affinity to DNA follows the order of 3 > 1> 2. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

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