• Title/Summary/Keyword: Macrocyclic Schiff base

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Synthesis and Physicochemical Properties of Schiff Base Macrocyclic Ligands and Their Transition Metal Chelates

  • Rafat, Fouzia;Siddiqi, K.S.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.912-918
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    • 2011
  • Tetraaza Schiff base macrocyclic ligands, $L^1$,$L^2$ and their transition metal chelates have been synthesized and characterized by elemental analyses, IR, electronic, EPR and $^1H$ NMR spectra, TGA and magnetic measurements. The molar conductance of one milli-molar solution of the complexes measured in DMF indicates that the divalent metal complexes are nonelectrolyte while those of trivalent metal ion, are 1:1 electrolytic in the same solvent. The reduction of Racah parameter from the free ion value confirms the presence of considerable covalence of metal ligand sigma bond in the Co(II) and Mn(II) complexes. The EPR spectra of Cu(II) complexes at room temperature shows axial symmetry indicating a $d_x{^2}_{-y}{^2}$ ground state with significant covalent character. The thermal analysis suggests that the complexes do not contain water molecules because only the metal is left as residue.

Synthesis and Characterization of Schiff Base Metal Complexes and Reactivity Studies with Malemide Epoxy Resin

  • Lakshmi, B.;Shivananda, K.N.;Prakash, Gouda Avaji;Isloor, Arun M.;Mahendra, K.N.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.473-482
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    • 2012
  • A novel malemide epoxy containing Co(II), Ni(II) and Cu(II) ions have been synthesized by curing malemide epoxy resin (MIEB-13) and Co(II), Ni(II) and Cu(II) complexes of macrocyclic bis-hydrazone Schiff base. The Schiff base was synthesized by reacting 1,4-dicarbnyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol. The Schiff base and its Co(II), Ni(II) and Cu(II) complexes have been characterized by elemental analyses, spectral (IR, $^1H$ NMR, UV-vis., FAB mass, ESR), thermal and magnetic data. The curing reaction of maleimide epoxy compound with metal complexes was studied as curing agents. The stability of cured samples was studied by thermo-gravimetric analyses and which have excellent chemical (acid/alkali/solvent) and water absorption resistance. Further, the scanning electron microscopy (SEM) and definitional scanning colorimetric (DSC) techniques were confirmed the phase homogeneity of the cured systems.

Antifungal Activities of Copper(II) with Biosensitive Macrocyclic Schiff Base Ligands Derived from 4-Aminoantipyrine Derivatives

  • Gopalakrishnan, S.;Joseph, J.
    • Mycobiology
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    • v.37 no.2
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    • pp.141-146
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    • 2009
  • Novel copper(II) complexes have been synthesized from the macrocyclic Schiff bases derived from Knoevenagel condensed ${\beta}$-ketoanilides (obtained by the condensation of acetoacetanilide and substituted benzaldehydes), 4-aminoantipyrine and ophenylene diamine. The structural features have been determined from their analytical and spectral data. All the Cu(II) complexes exhibit square planar geometry. Their high molar conductance values support their 1 : 2 electrolytic nature. The magnetic moment data provide evidence for the monomeric nature of the complexes. The X-band ESR spectra of the |$CuL^1$|$(OAc)_2$ in DMSO solution at 300 and 77 K were recorded and their salient features are reported. The in vitro biological screening effects of the investigated compounds were tested against the bacterial species Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris and Pseudomonas aeruginosa and fungal species Aspergillus niger, Rhizopus stolonifer, Aspergillus flavus, Rhizoctonia bataicola and Candida albicans by well diffusion method. A comparative study of inhibition values of the Schiff bases and their complexes indicate that complexes exhibit higher antimicrobial activity than the Schiff bases. Copper ions proved to be essential for the growth-inhibitor effect. The extent of inhibition appeared to be strongly dependent on the initial cell density and on the growth medium.

Template Synthesis of Polyaza Macrocyclic Copper(II) and Nickel(II) Complexes: Spectral Characterization and Antimicrobial Studies

  • Gurumoorthy, P.;Ravichandran, J.;Karthikeyan, N.;Palani, P.;Rahiman, A. Kalilur
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2279-2286
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    • 2012
  • The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-aminopropylamino)ethane produce the 12-membered $N_3O$ and 17-membered $N_4O$ macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear $N_3O$ and $N_4O$ copper(II) complexes show one irreversible oneelectron reduction wave at $E_{pc}=-1.35$ and -1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at $E_{pc}=-1.25$ and -1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at $E_{pa}=+0.84$ and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

Spectroscopic characterization of N,N'-bis(salicylidene)pentane-1,3-diamine nickel(II) complex

  • Kim, Gilhoon;Won, Hoshik
    • Journal of the Korean Magnetic Resonance Society
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    • v.18 no.2
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    • pp.74-81
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    • 2014
  • The $N_2O_2$ tetradentate Schiff base ligand, N,N'-bis(salicylidene)pentane-1,3-diamine (Salpn), coupled with 1:2 concentration ratio of 1,3-diaminopentane and salicylaldehyde was used to produce a series of macrocyclic Nikel(II) complexes. In the metal complexation, it was observed that Salpn macrocyclic ligand can adopt more than a metal ion giving an unique multinuclear metal complexes including Ni(II)Salpn and $Ni(II)_3(Salpn)_2$. Characteristic IR ${\upsilon}(M-O)$ peaks for Ni(II)Salpn and $Ni(II)_3(Salpn)_2$ were observed to be $1028cm^{-1}$ and $1024cm^{-1}$, respectively. Characteristic UV-Vis absorption ${\lambda}_{max}$ peaks for $Ni(II)_3(Salpn)_2$ were observed to be 241nm and 401 nm. Structural characterization of $Ni(II)_3(Salpn)_2$ by NMR exhibits that the salicylidene ring moiety has two different resonance signals originated from the magnetically asymmetric diligand and trinuclear bis complex. Complete NMR signal assignments and characterizations elucidating structural features of $Ni(II)_3(Salpn)_2$ were described in detail.

Synthesis and Characterization of Homo Binuclear Macrocyclic Complexes of UO2(VI), Th(IV), ZrO(IV) and VO(IV) with Schiff-Bases Derived from Ethylene diamine/Orthophenylene Diamine, Benzilmonohydrazone and Acetyl Acetone

  • Mohapatra, R.K.;Ghosh, S.;Naik, P.;Mishra, S.K.;Mahapatra, A.;Dash, D.C.
    • Journal of the Korean Chemical Society
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    • v.56 no.1
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    • pp.62-67
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    • 2012
  • A series of homo binuclear complexs of the type $[M_2(L/L^')(NO_3)n].mH_2O$, [where $M=U{O_2}^{2+},\;Th^{4+},\;ZrO^{2+}$] and $[(VO)_2(L/L^')(SO_4)_2]{\cdot}2H_2O$, L=1,5,6,9,12,15,16,20 octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (OTTDO) or L'=10:11;21:22-dibenzo-1,5,6,9,12,15,16,20-octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (DOTTOT), n=4 for $U{O_2}^{2+}$, $ZrO^{2+}$ n=8 for $Th^{4+}$ m=1,2,3 respectively, have been synthesized in template method from ethylenediamine/orthophenylene diamine, benzil monohydrazone and acetyl acetone and characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, $^1H$-NMR studies. The results indicate that the VO(IV) ion is penta co-ordinated yielding paramagnetic complexes; $UO_2(VI)$, ZrO(IV) ions are hexa co-ordinated where as Th(IV) ion is octa co-ordinated yielding diamagnetic complexes of above composition. The fungi toxicity of the ZrO(IV) and VO(IV) complexes against some fungal pathogen has been studied.

Synthesis and Characterization of UO2(VI), Th(IV), ZrO(IV) and VO(IV) Complexes with Schiff-Base Octaazamacrocyclic Ligands (Schiff-염기인 옥타아자-거대고리 리간드의 UO2(VI), Th(IV), ZrO(IV) 및 VO(IV) 착물 합성 및 특성)

  • Mohapatra, Ranjan Kumar;Dash, Dhruba Charan
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.395-401
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    • 2010
  • A series of macrocyclic complexes of the type [M(L/L')$(NO_3)_n$].$mH_2O$ and [VO(L/L')($SO_4$)].$2H_2O$, where L/L' is a Schiff base "3,4,10,11-tetraphenyl/tetramethyl-1,2,5,6,8,9,12,13-octaaza cyclotetradeca-2,4,9,11-tetraene-7,14-dithione" derived from thiocarbohydrazide (TCH), benzilmonohydrazone (BMH)/diacetylmonohydrazone (DMH) and carbon disulphide, M = $UO_2$ (VI), Th(IV) and ZrO(IV), n = 2, 4, m = 2, 3, have been synthesized via metal ion template methods. The complexes are characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared and $^1H$-NMR spectral studies. The ESR and cyclic voltammetry studies of the vanadyl complexes have been carried out. The results indicate that the VO(IV) ion is penta-coordinated yielding paramagnetic complexes; $UO_2$(VI) and ZrO(IV) ions are hexacoordinated where as Th(IV) ion is octa-coordinated yielding diamagnetic complexes of above composition.

Halide (Cl-, Br-, I-) Influence on the Electronic Properties of Macrocyclic Nickel(II) Complexes: Ab-initio DFT Study

  • Zarei, Seyed Amir;Akhtari, Keivan;Hassanzadeh, Keyumars;Piltan, Mohammad;Saaidpour, Saadi;Abedi, Marjan
    • Journal of the Korean Chemical Society
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    • v.57 no.3
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    • pp.311-315
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    • 2013
  • The geometry structures of hexa-coordinated [NiLX]X complexes ($X=Cl^-,\;Br^-,\;I^-$) {L = 8,9,18,19-tetrahydro-7H,17H-dibenzo[f,o] [1,5,9,13]dioxadiaza cyclohexadecine-8,18-diol} are optimized by density functional theory (DFT) using B3LYP/LANL2DZ. The calculated geometric parameters are in good agreement with the corresponding experimental values. Calculation results about these complexes show that dipole moment decreases, and the energy levels of HOMOs descend from iodo-complex to chloro-complex. The energy levels of HOMOs descend gently from iodo-complex to chloro-complex, while the energy levels of LUMOs in the present complexes are almost similar; therefore the energy gapes between HOMOs and LUMOs increased from iodo-complex to chloro-complex.