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1.
Reaction of tridentate Schiff bases with nickel and cadmium salts in methanol afforded two new mononuclear complexes, [Ni(L1)2] (I) and [Cd(L2)2] (II), where L1 and L2 are the anions of 2-bromo-4-chloro-6-[(3-dimethylaminopropylimino)methyl]phenol (HL1) and 2-bromo-4-chloro-6-[(3-morpholin-4-ylpropylimino)methyl]phenol (HL2), respectively. The complexes were characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1428653 (I) and 1428654 for (II)), FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2 1/c, with a = 8.8216(8), b = 14.0424(8), c = 11.8687(12) Å, β = 111.238(2)°, V = 1370.4(2) Å3, Z = 2. Complex II crystallizes in the monoclinic space group P2 1/n, with a = 9.6774(4), b = 15.8970(6), c = 20.3144(7) Å, β = 90.408(2)°, V = 3125.1(2) Å3, Z = 4. The metal atoms in the complexes are coordinated by two tridentate Schiff base ligands, forming octahedral coordination. The free Schiff bases and the complexes were assayed for antibacterial activities. Both complexes are more active against the bacteria than the free Schiff bases. Complex II has the MIC value of 0.39 μg mL–1 against Bacillus subtilis.  相似文献   

2.
This paper describes the hydrothermal synthesis, full characterization, and architectural diversity of three intriguingly bioactive cobalt–organic frameworks, namely, 3D [Co(HL ? )2(BPY)] n ·4nH2O (1), 2D [Co(HL ? )2(BPE)] n (2), and 2D [Co(HL ? )2(DPP)] n (3) coordination polymers, synthesized through a mixed ligand strategy using H 2 L (1-H-indazole-3-carboxylic acid) as a main structural block and the flexible bipyridine and its derivatives (BPY = 4,4′-bipydine, BPE = 1,2-bis(4-pyridyl)ethane, DPP = 1,3-bis(4-pyridyl)propane) as auxiliary ligand sources. Complexes 13 were isolated as air stable and slightly soluble crystalline solids and characterized using elemental analysis, FT-IR, electrochemical technique, thermogravimetric analysis, powder X-ray diffractometer, and single-crystal X-ray crystallography. The bipyridine derivatives played key roles in defining the structural space group and dimensionality feature of the obtained networks. The abundant H-bonding and ππ stacking interactions in complexes 13 gave rise to their intricate metal–organic structures of 3D (1), 2D (2), and 2D (3). In addition, the solutions of complexes 13 showed profound antifungal activities against the selected strain of Colletotrichum musae compared with the controlled group using benomyl as a traditional agrochemical fungicide.  相似文献   

3.
Metal(II) complexes of 4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (HL) were prepared, and their compositions and physicochemical properties were characterized on the basis of elemental analysis, with1HNMR, UV–Vis, IR, mass spectroscopy and thermogravimetric analysis. All results confirm that the novel complexes have a 1:1 (M:HL) stoichiometric formulae [M(HL)Cl2] (M = Cu(II)(1), Cd(II)(5)), [Cu(L)(O2NO)(OH2)2](2), [Cu(HL)(OSO3)(OH2)3]2H2O(3), [Co(HL)Cl2(OH2)2]3H2O(4), and the ligand behaves as a neutral/monobasic bidentate/tridentate forming a five/six-membered chelating ring towards the metal ions, bonding through azomethine nitrogen, exocyclic carbonyl oxygen, and/or deprotonated phenolic oxygen atoms. The XRD studies show that both the ligand and Cu(II) complex (1) show polycrystalline with monoclinic crystal structure. The molar conductivities show that all the complexes are non-electrolytes. On the basis of electronic spectral data and magnetic susceptibility measurements, a suitable geometry has been proposed. The trend in g values (g ll > g  > 2.0023) suggest that the unpaired electron on copper has a \(d_{{x^{2} - y^{2} }}\) character, and the complex (1) has a square planar, while complexes (2) and (3) have a tetragonal distorted octahedral geometry. The molecular and electronic structures of the ligand (HL) and its complexes (15) have been discussed. Molecular docking was used to predict the binding between HL ligand and the receptors of the crystal structure of Escherichia coli (E. coli) (3t88) and the crystal structure of Staphylococcus aureus (S. aureus) (3q8u). The activation thermodynamic parameters, such as activation energy (E a), enthalpy (ΔH), entropy (ΔS), and Gibbs free energy change of the decomposition (ΔG) are calculated using Coats–Redfern and Horowitz–Metzger methods. The ligand and its metal complexes (15) showed antimicrobial activity against bacterial species such as Gram positive bacteria (Bacillus cereus and S. aureus), Gram negative bacteria (E. coli and Klebsiella pneumoniae) and fungi (Aspergillus niger and Alternaria alternata); the complexes exhibited higher activity than the ligand.  相似文献   

4.
The synthesis and thermal behavior of the new [Pd(fum)(bipy)] n ·2nH2O (1), [Pd(fum)(bpe)] n ·nH2O (2) and [Pd(fum)(pz)] n ·3nH2O (3) {bipy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and 13C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46–491 °C. In all the cases, metallic palladium was identified as the final residue.  相似文献   

5.
LRM (Low Rank Modification) is a mathematical method that produces eigenvalues and eigenstates of generalized eigenvalue equations. It is similar to the perturbation expansion in that it assumes the knowledge of the eigenvalues and eigenstates of some related (unperturbed) system. However, unlike perturbation expansion, LRM produces correct results however large the modification of the original system. LRM of finite-dimensional systems is here generalized to the combined (external and internal) modifications. Parent n-dimensional system A n containing n eigenvalues λ i and n eigenstates \({| {\Phi_i}\rangle}\) is described by the generalized n × n eigenvalue equation. In an external modification system A n interacts with another ρ-dimensional system B ρ which is situated outside the system A n . In an internal modification relatively small σ-dimensional subsystem of the parent system A n is modified. Modified system C n+ρ that contains external as well as internal modifications is described by the generalized (n + ρ) × (n + ρ) eigenvalue equation. This system has (n + ρ) eigenvalues \({\varepsilon_s}\) and (n + ρ) corresponding eigenstates \({| {\Psi_s}\rangle}\) . In LRM this generalized (ρn) × (ρn) eigenvalue equation is replaced with a (nonlinear) (ρ + σ) × (ρ + σ) equation which produces all eigenvalues \({\varepsilon_s \notin \left\{ {\lambda_i}\right\}}\) and all the corresponding eigenstates \({| {\Psi_s}\rangle }\) of C n + ρ. Another equation produces remaining solutions (if any) that satisfy \({\varepsilon_s \in \left\{ {\lambda_i}\right\}}\) . Those two equations produce exact solution of the modified system C n + ρ. If (ρσ) is small with respect to n, this approach is numerically much more efficient than a standard diagonalization of the original generalized eigenvalue equation. Unlike perturbation expansion, LRM produces exact results, however large modification of the parent system A n .  相似文献   

6.
Differential scanning calorimetry (DSC) was used to investigate the thermal behavior and non-isothermal crystallization kinetics of the Fe67Nb5B28 metallic glasses prepared by melt-spinning method. DSC traces exhibit that the crystallization takes place through a single exothermic reaction, and it processes a good thermal stability in thermodynamics. The activation energies for nucleation and grain growth processes were calculated to be 536 ± 22 and 559 ± 20 kJ mol?1 by Kissinger equation, respectively, and 551 ± 24 and 574 ± 20 kJ mol?1 by Ozawa equation, respectively. It means that the grain growth process is more difficult than the nucleation process. The variation of local Avrami exponent n(x) with crystallized fraction x demonstrates that the crystallization mechanism varies at different stages. The n(x) is larger than 2.5 at the initial stage of 0 < x < 0.3, implying a mechanism of diffusion-controlled three-dimensional growth with increasing nucleation rate. The n(x) decreases from 2.5 to 1.5 in the range of 0.3 < x < 0.65, suggesting that the crystallization belongs to three-dimensional nucleation and grain growth with decreasing nucleation rate. And n(x) lies between 1.0 and 1.5 in the range of 0.65 < x < 0.95, indicating that the crystallization corresponds to the growth of particles with an appreciable initial volume. Low-temperature annealing corresponds to the precipitation of α-Fe, Fe2B, and Fe23B6 phases, and further annealing leads to the formation of α-Fe, Fe2B, and FeNbB phases. The magnetic properties in relation to microstructure change of the Fe67Nb5B28 metallic glasses are discussed.  相似文献   

7.
The N-(2-pyridyl) 4-toluene sulfonamide as a free ligand (PTS) was prepared from the reaction of 2-amino pyridine and 4-toluenesulfonyl chloride in the presence of potassium hydroxide solution 1 M as a base and THF was used as a solvent. The complex tetrakis [N-(2-pyridyl) sulfonamide] di palladium (1) (Pd2L4) was also prepared from the reaction of PdCl2(CH3CN)2 using (PTS) in the presence of NaOH 0.5 M and its application in Heck and Suzuki reactions. This complex consists of a binuclear unit consisting of four ligands linked to two palladium atoms via the nitrogen of pyridines ring and the nitrogen of sulfonamides. These compounds were confirmed by FT-IR and 1H NMR spectroscopy. Moreover, the structure of the complex was studied by single-crystal X-ray diffraction method. The green crystal of Pd2L4 [L = N-(2-pyridyl) sulfonamide](1) was found to crystallize in the monoclinic space group C2/c with a = 18.2013(19), b = 19.7544(16), c = 17.2898(19) Å, β = 120.179(8) °; V = 5374.0(9) Å3; Z = 4; the final R 1 = 0.0894, wR 2 = 0.1754 (or 5867 observed reflections and 318 variables). The Pd–Pd distance is 2.567(2) Å. In addition, PTS and Pd2L4 presented different antibacterial behaviors. The free ligand was active against Staphylococcus aureus and Escherichia coli, but the complex was inactive against them.  相似文献   

8.
A silver(I) complex of saccharinate (sac) with pyrazine (pyz), [Ag(sac)(pyz)] n , has been synthesized and characterized by elemental analysis, IR, thermal analysis, and single-crystal X-ray diffractometry. The complex crystallizes orthorhombic space group Pnma with unit cell parameters of a = 13.0073(9) Å, b = 6.4907(6) Å, c = 13.4007(9) Å, V = 1131.37(15) Å3, and Z = 4. [Ag(sac)(pyz)] n is a one-dimensional coordination polymer, in which the sac ligand acts as a monodentate ligand through the N atom and the trigonal silver centers are linked by the bridging pyz ligands. The individual chains are connected into two-dimensional supramolemular network by aromatic π(sac)···π(pyz) stacking interactions. The FTIR spectrum of [Ag(sac)(pyz)] n has been recorded in the region and 4,000–400 cm?1. The optimized geometry, frequency, and intensity of the vibrational bands of [Ag(sac)(pyz)] n were obtained by density functional theory (DFT) at the B3LYP level. The vibrational frequencies were calculated and the scaled values have been compared with the experimental FTIR data. The observed and calculated frequencies are found to be in good agreement.  相似文献   

9.
A coordination polymer of formula [Cu(μ 1,3-N3)2(imH)2] n (1) has been synthesized by reaction of Cu(NO3)2 with imidazole and sodium azide in CH3OH/CH3CN. The complex was characterized by FTIR, elemental analysis, powder diffraction, thermogravimetric analysis, magnetic measurements, and single-crystal X-ray diffraction. The X-ray crystal structure shows that the Cu(II) centers have a distorted octahedral coordination geometry, being coordinated by two imidazole ligands at the trans positions. Each azide links two [Cu(imH)2]2+ units to form 1D zigzag chains. Variable-temperature magnetic susceptibility studies at low field reveal dominant intrachain ferromagnetic/antiferromagnetic interactions. Using a model with n = 10, the coupling parameters J AF = ?2.95 and J F = 17.99 with g = 2.12 have been determined.  相似文献   

10.
The Cu, Ni, and Со complexes based on the following new azomethine compounds containing azobenzene groups in the ortho- or para-positions of the amine fragment are synthesized: 2-allyl-6-[(E)-[4-(E)-phenylazophenyl]iminomethyl]phenol (HL1), 2-allyl-6-[(E)-[4-methyl-2-[(E)-phenylazo]-p-tolylazo] iminomethyl]phenol (HL2), 5-methoxy-2-[(E)-[4-[(E)-phenylazo]phenyl]iminoethyl]phenol (HL3), and 5-methoxy-2-[(E)-[4-methyl-2-[(E)-p-tolylazo]phenyl]iminomethyl]phenol (HL4). The structures of the complexes are determined by the data of IR and 1Н NMR spectroscopy (for the azomethine compounds), X-ray absorption spectroscopy, and magnetochemistry. The coordination centers of all Cu complexes have a distorted square structure. A direct dependence of the geometry of the coordination polyhedron on the position of azobenzene groups in the amine fragments of the ligands is found for the Ni and Co complexes. The octahedral environment of the nickel and cobalt ions takes place in the case of the ortho-position of the amine fragment, whereas the square environment for the Ni complexes or the tetrahedral environment for the Co complexes is observed at the para-position. The molecular structures of two azomethines HL1 and HL4 are determined by X-ray diffraction analysis (CIF files CCDC nos. 1552836 (HL1) and 1552837 (HL4)).  相似文献   

11.
A series of organotin(IV) complexes of type R2SnLCl [R = Ph, Bu, Et, Me] were prepared by reaction of diorganotindichloride(IV) with Schiff base ligands, L1 = (1-[(6-ethoxy-benzothiazol-2-ylimino)-methyl]-naphthalen-2-ol), L2 = (1-[(6-nitro-benzothiazol-2-ylimino)-methyl]-naphthalen-2-ol), L3 = (1-[(6-methoxy-benzothiazol-2-ylimino)-methyl]-naphthalen-2-ol) and L4 = (1-[(6-methyl-benzothiazol-2-ylimino)-methyl]-naphthalen-2-ol) obtained from 2-amino-6-substituted benzothiazole derivatives with 2-hydroxy-1-naphthaldehyde in 1:1 molar ratio. These organotin(IV) complexes were characterized by various spectroscopic techniques (1H, 13C and 119Sn NMR, FT-IR), and physical techniques (X-ray powder diffraction analysis and elemental analysis). The coordination of the prepared complexes has been planned as pentacoordinated around the central tin atom during which ligands coordinated to tin atom in bidentate manner acted as N, O donor system. The ligands and their complexes were screened for antibacterial and antifungal activities against Gram-positive bacteria Bacillus cereus (MTCC 10072), Staphylococcus aureus (NCIM 2901), Gram-negative bacteria Escherichia coli (MTCC 732), Pseudomonas aeruginosa (MTCC 424) and fungi Aspergillus niger (MTCC 9933) and Aspergillus flavus (ATCC 76801). The output of QSAR analysis indicated that topological parameters (molecular connectivity indices) were responsible for controlling the antimicrobial activity of the synthesized compounds.  相似文献   

12.
The (HL n )2[CuCl4] complexes (where L n are organic nitrogen-containing bases with n = 1–6) were synthesized. The crystal and molecular structures of bis(2-methylimidazolium) tetrachlorocuprate(II), (HL1)2[CuCl4], were determined. The spectral characteristics of the complexes were measured. The correlations between the degree of distortion of the crystal structure of the tetrachlorocuprate anion and the hydrogen bond parameters and the spectral characteristics of compounds were obtained.  相似文献   

13.
Reaction between hydrazine derivative ligands (HrzE) or (HrzB) and chromium salt in 1:2 (metal:ligand) molar ratio yielded monometallic trivalent coordination compounds with general formula [Cr(HrzE)2X2]X and [Cr(HrzB)2X2]X, where (HrzE) = hydrazine carboxylic acid ethyl ester, (HrzB) = hydrazine carboxylic acid tert-butyl ester, and X = Cl?, Br? or F?. Elemental analysis, conductivity measurements, magnetic moment measurements, and various spectroscopic techniques, viz. infrared, ultraviolet–visible, and electrospray ionization mass spectrometry, were applied to illustrate the structure and composition of the coordination compounds. Analytic and conductivity results were consistent with 1:1 electrolytic behavior and the proposed formulas of the coordination compounds. Electronic absorption data and magnetic moment parameters indicated octahedral geometry surrounding the metal ion in the coordination compounds. The in vitro antimicrobial behavior of the ligands and coordination compounds was screened using four bacterial strains (Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Salmonella typhi) and two fungal strains (Candida parapsilosis and Saccharomyces cerevisiae). The results indicated improved activity of the coordination compounds compared with the free ligands against the studied bacteria and fungi.  相似文献   

14.
The complexes [Ni(L1)(pyc)2]·2H2O (1) (L1 = C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; Hpyc = pyrazinecarboxylic acid) and [Cu(L2)(H-cpdc)] (2) (L2 = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane; H2-cpdc = cyclopropanedicarboxylic acid) have been synthesized and structurally characterized. The crystal structure of complex 1 shows a distorted octahedral coordination geometry around the nickel(II) center, with four secondary amines in the equatorial positions and two nitrogen atoms of the pyc? ligands in the trans positions. In complex 2, the coordination environment around the copper(II) center is a Jahn–Teller distorted octahedron with four Cu–N bonds and two axial Cu–O bonds. The electronic spectra, electrochemical and TGA behavior of the complexes are significantly affected by the nature of the axial pyc? and H-cpdc? ligands.  相似文献   

15.
The structural features of 38 mononuclear d 2-Re(V) octahedral monooxo complexes (I–XXXVIII) with oxygen atoms of bidentate-chelating (O, P) ligands (L n ) are considered. The atoms O(L n ) are mostly in trans positions to O(oxo) ligands. In three compounds of general formula [ReO(Lmono)(L n )2] (XXXVI–XXXVIII), the O atoms of two L n ligands occupy both trans and cis positions to oxo ligands. In one complex, namely, in [ReO(L n )(L tri 11 )], n = 3 (XXXV), the atom O(L3) is in the cis position to the oxo ligand; the trans position to O(oxo) is occupied by the atom O(L tri 11 ).  相似文献   

16.
In an attempt to find single-source precursors, a series of small clusters of inorganic azides of indium (Br2InN3) n (n = 1–6) were studied using the dispersion correction density functional theory (wB97XD). The obtained (Br2InN3) n (n = 2–6) clusters have the core structures of 2n-membered ring with alternating indium and α-nitrogen atoms. The influences of cluster size (oligomerization degree n) on the structures, energies, IR spectra, and thermodynamic properties of clusters were discussed. The computed binding energies indicate the stability: 3A > 3B, 4B > 4C > 4A > 4D, 5E > 5D > 5B = 5C > 5A and 6I > 6C > 6D > 6G ≥ 6H > 6F > 6E > 6B > 6A. It is also found that (Br2InN3)2 and (Br2InN3)4 clusters possess higher stability than their neighbor sizes judged by the calculated second-order difference of energies (Δ2 E). Meanwhile, thermodynamic properties for (Br2InN3) n (n = 1–6) clusters increase with the increasing temperature and oligomerization degree n, and the oligomerizations are thermodynamically favorable at temperatures up to 800 K.  相似文献   

17.
The synthesis, IR and Raman spectroscopic study, and X-ray diffraction analysis of [Ni(HL1)3](L2)2 · 4H2O (I), where HL1 is phenylacetic acid hydrazide and L2 is the benzoate monoanion, have been performed. The structural units of a crystal of complex I are complex [Ni(HL1)3]2+ cations, (L2) anions, and crystallization water molecules. The nickel atom is coordinated to the three oxygen atoms at octahedron apices and the three nitrogen atoms of three bidentate chelate (О, N) ligands HL1 in cis,trans-meredianal (fac) conformation. The structural units of a crystal of complex I are bonded by a branched network of О–Н···О and N–H···O hydrogen bonds.  相似文献   

18.
The reaction of cyclopentylamine with 2-hydroxy-1-naphthaldehyde and 5-nitrosalicylaldehyde, respectively, in methanol affords two new Schiff bases, 1-(cyclopentyliminomethyl)naphthalen-2-ol (HL1) and 4-nitro-2-(cyclopentyliminomethyl)phenol (HL2). Two new zinc(II) complexes, [Zn(L1)2] (I) and [Zn(L2)2] (II), derived from the Schiff bases, have been prepared and characterized by single-crystal X-ray diffraction, FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P21/c with a = 17.834(4), b = 14.738(3), c = 9.868(2) Å, β = 91.20(3)°, V = 2593.1(9) Å3, Z = 4. Complex II crystallizes in the triclinic space group P \(\bar 1\) with a = 10.206(1), b = 10.502(1), c = 12.554(1) Å, α = 66.771(2)°, β = 78.133(2)°, γ = 76.292(2)°, V = 1191.8(1) Å3, Z = 2. The Zn atom in each complex is coordinated by two N and two O atoms from two Schiff base ligands, forming a tetrahedral geometry. The Schiff bases and the complexes were assayed for antibacterial activities.  相似文献   

19.
The reactions of aromatic dicarboxylic acids and methyl-functionalized 4,4′-bipyridine ligands with metal salts under hydrothermal conditions generated four structurally diverse cobalt(II), zinc(II) and cadmium(II) coordination polymers, [Co(CH3-BDC)(dmbpy)0.5] n (1), [Cd(OH-HBDC)2(dmbpy)] n (2), [Zn(NDC)(dmbpy)] n , (3) and {[Cd(DBA)(dmbpy)0.5]·2H2O} n (4) (CH3–H2BDC = 5-methylisophthalic acid, OH–H2BDC = 5-hydroxyisophthalic acid, H2NDC = 1,4-naphthalenedicarboxylic acid, H2DBA = 4,4′-methylenedibenzoic acid, dmbpy = 2,2′-dimethyl-4,4′-bipyridine). All four complexes have been structurally characterized by X-ray crystallography. Complex 1 shows a 3D jsm topology structure with two 1D channels parallel to the a and b axes. Complex 2 has a zigzag chain in which the OH-HBDC ligands point alternately up and down. Complexes 3 and 4 show 2D (4,4) networks when the dinuclear metal centers and their ligands are regarded as nodes and linkers, respectively. Complex 3 also shows twofold interpenetration with 1D channels along the b axis. Two nets of complex 4 interlock in parallel, giving rise to a polycatenated layer (2D → 2D). Thermogravimetric and chemical stabilities, magnetic and luminescent properties of these complexes were investigated.  相似文献   

20.
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B?) in the presence of tetraisopropyl methylene diphosphonate [T(iPr)MDP, L] has been investigated. The equilibrium data have been explained assuming that the complexes HL+, HL2 +, ML2 3+, ML3 3+ and ML4 3+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuL n 3+ and AmL n 3+, where n = 2, 3, 4 and L is T(iPr)MDP, in water-saturated nitrobenzene are comparable.  相似文献   

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