Synthesis, Thermal, Electrical and Catalytic Studies of Some Transition Metal Polychelates of Bis-bidentate Schiff Base

Polychelates of Mn（Ⅱ）, Fe（Ⅱ）, Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） with the bis salen-type ligand derived from 4,4＇-bis[（salicylaldehyde-5）azo]biphenyl and 1,4-diaminobutane have been synthesized. All the polychelalls have been characllrized by elemental analysis, magnetic susceptibility measurements, IR, electronic spectra and thennogravirncuic studies. All the complexes isolated in solid stall are dark coloured and insoluble in water and common organic solvents. The ligand behaves as a bis-bidentall molecule coordinating through the phenolic oxygen and azomethine nitrogen atoms. The thermal decomposition of these metal complexes was investigated by thermogravimetric analysis and data have been analyzed for kinetic parameters using Broido equation. The solid-state electrical conductivity of the ligand and its polychelalls in the form of compressed pellet was studied in the temperaturc range from 313 to 413 K All the polychelalls were found to show semiconducting nature. The Mn（Ⅱ）, Fe（Ⅱ）, Co（Ⅱ） and Ni（Ⅱ） polychelalls have been assessed for the catalytic epoxidation of styrene.     

Synthesis,characterization and anti-microbial studies of a newly developed polymeric Schiff base and its metal-polychelates

A new polymeric Schiff base containing formaldehyde and piperazine moieties has been synthesized by condensation of salicylaldimine, formaldehyde and piperazine in alkaline medium; its metal polychelates have also been synthesized with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) acetate. The synthesized Schiff base and its metal polychelates were characterized by elemental, spectral (IR, ¹H NMR, UV-visible) and thermogravimetric analysis (TGA). Electronic spectra and magnetic moments indicate that Mn(II), Co(II) and Ni(II) polychelates show octahedral geometry, while Cu(II) and Zn(II) polychelates show square planar and tetrahedral geometry, respectively. All compounds show excellent anti-bacterial as well as anti-fungal activity against three bacteria and two fungi. The anti-microbial activities were determined by using agar well diffusion method, with 50 µg mL^?1 and 100 µg mL^?1 concentration of each compound tested against the microbes.     

Synthesis,spectral, and antibacterial screening studies of chelating polymers of bisphenol-A–formaldehyde resin bearing barbituric acid

A new polymeric ligand was synthesized by the reaction of bisphenol-A and formaldehyde in the basic medium, followed by condensation polymerization with barbituric acid in the acidic medium. Polymer metal complexes were prepared by reaction of this resin with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II). The polymeric resin and its metal polychelates were characterized by elemental analysis, FT-IR, ¹³C-NMR, and ¹H-NMR spectra. The geometry of the polymer metal complexes was evaluated by electronic spectra (UV-Vis) and magnetic moment measurement. Thermal stabilities show an increased thermal stability of the metal polychelates compared to the ligand. The antibacterial activities of all the synthesized polymers were investigated against Bacillus subtilis, Staphylococcus aureus, and Escherichia coli, showing good antibacterial activities against these bacteria. Cu(II) polychelate showed highest biocidal activity.     

Polymer complexes. LV. Spectroscopic,thermal studies,and coordination of metal ions N-[3-(5-amino-1,2,4-triazolo)] acrylamide polymer complexes

Novel polymeric complexes with a potentially bidentate ligand formed by amidation of 3,5-diamino-1,2,4-triazole with acryloyl chloride were synthesized and characterized on the basis of elemental analyses, IR, ¹H-NMR, UV-Vis, magnetic susceptibility measurements, molar conductance, and thermal analyses. The molar conductance data reveal that all the polymer complexes are non-electrolytes. Spectral studies reveal that the free ligand coordinates bidentate to the metal ion through the oxygen of the carbonyl and azomethine of the heterocyclic ring. Elemental analyses of the polychelates indicate the metal to ligand ratio of 1?:?1/1?:?2. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each polymeric complex. The electron spin resonance spectral data of the Cu(II) complex showed that the metal–ligand bonds have considerable covalent character. The thermal behavior of these chelates shows that the polymer complexes lose coordinated water in the first step immediately followed by decomposition of the anions and ligand molecules in a subsequent step.     

Synthesis,characterization, ion-exchange and antimicrobial study of poly[(2-hydroxy-4-butoxy benzophenone)ethylene] resin and its polychelates with lanthanides

The polymeric ligand (resin) was prepared from 2-hydroxy-4-butoxy benzophenone with ethane diol with polyphosphoric acid as catalyst on constant heating at 160°C for 13 h. The poly[(2-hydroxy-4-butoxy benzophenone)ethylene] (HBBP-ED) forms 1 : 2 metal : ligand polychelates with La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III). The polymeric ligand and its polychelates were characterized by elemental analyses, electronic spectra, magnetic susceptibilities, IR-spectroscopy, NMR and thermogravimetric analyses. The molecular weight was determined using number average molecular weight (M n) by a vapor pressure osmometry (VPO) method. All the polychelates are paramagnetic except La(III). Ion-exchange studies at different electrolyte concentrations, pH and rate have been carried out for the lanthanide ions. The resin can be used as an ion-exchanger and antimicrobial agent.     

Kinetics of Free Radical Polymerization. XXXVIII. Solvent Effect on the Degree of Polymerization of Poly(ethyl Acrylates) and Poly(methyl Acrylates)

Abstract

Polychelates of VO(II), Mn(II), Zn(II), Cr(III), and Fe(III) with the bis-oxime of 5, 5′-methylene-bis-salicylaldehyde have been prepared and are characterized on the basis of their elemental analyses, IR, diffuse reflectance spectra, magnetic moments, and thermogravimetric analyses. Except for VO(II), the other metal ions form octahedral polychelates. VO(II) forms a square-pyramidal coordination polymer. The Zn(II) poly-chelate has the highest thermal stability.     

Synthesis,Characterization, Thermal and Antimicrobial Activity of Poly[(2‐Hydroxy‐4‐methoxy benzophenone)propylene] and its Polychelates with Lanthanides(III)

The polymeric ligand (resin) was prepared from 2‐hydroxy‐4‐methoxy‐benzophenone with propylene glycol in the presence of polyphosphoric acid as a catalyst at 160°C for 13 h. The poly[(2‐hydroxy‐4‐methoxybenzophe‐none) propylene] H(HMBP‐PG) form 1:2 metal:ligand chelates with La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III) and Dy(III). The polymeric ligand and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR‐spectroscopy, NMR, and thermogravimetric analyses. The molecular weight was determined using Number Average Molecular Weight (Mn) by a Vapor Pressure Osmometry (VPO) method. All the polychelates are paramagnetic in nature. The resin and their polychelates were tested for antimicrobial activity against E. coli, B. substilis, S. aureus (bacteria) and S. cerevisiae (yeast). It is found that the synthesized polychelates can be used as antibacterial agents.     

Physicochemical characterization,thermal, and electrical conductivity studies of some transition metal complexes of bis-chelating Schiff base

Polychelates of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and VO(IV) with a new bis-chelating Schiff base derived from 5-acetyl-2,4-dihydroxyacetophenone and isonicotinic acidhydrazide have been synthesized. The resulting polychelates have been characterized by elemental analyses, IR and electronic spectral data, magnetic susceptibility measurements and thermogravimetric analysis. All the polychelates are dark coloured solids and insoluble in water and common organic solvents. Thermogravimetric analyses confirm coordination of water in complexes. Various kinetic and thermodynamic parameters have been evaluated from thermal data. The ligand acts as a bis-tridentate molecule coordinating through deprotonated phenolic/enolic oxygen atoms and azomethine nitrogen atoms. The solid-state conductivity of ligand and its polychelates have been measured in their compressed pellet form and all compounds were found to be semiconducting in nature.     

Characterization and Thermal Study of Schiff-Base Monomers and Its Transition Metal Polychelates and Their Photovoltaic Performance on Dye Sensitized Solar Cells

Azo dye monomer 4,4′-(4,4′-biphenylylenebisazo)-disalicylaldehyde-4n-butylphenyl aniline (H₂A) is synthesised by the reaction of 4,4′-bis[(salicylaldehyde-5)-azo]biphenyl (Azo) and n-butylaniline in the 1:2 molar ratio and its metal polychelates are also synthesized with Co(II), Ni(II), Cu(II), and Zn(II) metal ions. The synthesized compounds are characterized by ¹H, ¹³C NMR, Fourier transform infrared (FT-IR) spectroscopy, electronic spectra (UV-Vis), elemental analysis (C, H, N, O), gas chromatography-mass (GCmass) spectrometry, magnetic susceptibility and molar conductivity techniques. Thermal properties of the title compounds are studied using the thermogravimetric analysis (TGA). The metal molar ratio in all of the polychelates is found to be consistent with 1:1 (metal/ligand) stoichiometry. The influence of organic dyes H₂A and the [CuA(H₂O)₂] _n polychelate are investigated as photosensitizers on the photovoltaic parameters by current–voltage (I–V) measurements on TiO₂ photoelectrode dye sensitized solar cells (DSSCs). The [CuA(H₂O)₂] _n metal polychelate demonstrates the best performance as compared to the cell sensitized with H₂A.     

Thermal, catalytic and antimicrobial aspects of polychelates of phenolic resin with lanthanides (III)

The polymeric ligand (resin) was synthesized by condensation of 2-hydroxy-4-ethoxybenzophenone with 1,2-propylene glycol in presence of polyphosphoric acid as a catalyst at 150 °C for 10 h. The resin and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, Fourier transform infrared spectroscopy (FTIR), NMR and thermogravimetric analyses. Morphological Study of resin and polychelates were carried out by scanning electron microscope (SEM). The number average molecular weight was determined using vapor pressure osmometry (VPO) method. Antimicrobial activity of polychelates and catalytic activity of selected polychelates in organic synthesis have been studied. It was observed that, polychelates were found efficient catalysts and effective antimicrobial agents.     

Preparation, spectral and biological investigation of formaldehyde-based ligand containing piperazine moiety and its various polymer metal complexes

A novel tetradentate salicylic acid-formaldehyde ligand containing piperazine moiety (SFP) was synthesized by condensation of salicylic acid, formaldehyde and piperazine in presence of base catalyst, which was subjected for the preparation of coordination polymers with metal ions like manganese(II), cobalt(II), copper(II), nickel(II) and zinc(II). All the synthesized polymeric compounds were characterized by elemental analysis, IR, (1)H NMR and electronic spectral studies. The thermal stability was determined by thermogravimetric analysis and thermal data revealed that all the polymer metal complexes show good thermal stability than their parent ligand. Electronic spectral data and magnetic moment values revealed that polymer metal complexes of Mn(II), Co(II) and Ni(II) show an octahedral geometry while Cu(II) and Zn(II) show distorted octahedral and tetrahedral geometry respectively. The antimicrobial screening of the ligand and coordination polymers was done by using Agar well diffusion method against various bacteria and fungi. It was evident from the data that antibacterial and antifungal activity increased on chelation and all the polymer metal complexes show excellent antimicrobial activity than their parent ligand.     

A modern technique for preparation of zinc(II) and nickel(II) nanometric oxides using Schiff base compounds: synthesis,characterization, and antibacterial properties

The purpose of the work reported in this paper was the preparation and characterization of Zn(II) and Ni(II) nanometric oxides by using a simple Schiff compound as precursor for complexation then thermal degradation at 600 °C. Metal complexes [Ni(L)₂(Cl)₂] and [Zn(L)₂](NO₃)₂, where L is the Schiff base formed by condensation of 2-thiophenecarboxaldehyde with phenylhydrazine, were prepared and characterized by elemental analysis and by magnetic and spectroscopic measurements (infrared, Raman, X-ray powder diffraction, and scanning electron microscopy). Elemental analysis of the chelates suggests the stoichiometry is 1:2 (metal–ligand). Infrared spectra of the complexes are indicative of coordination of the nitrogen of the phenylhydrazine (–Ph–NH–) group and the sulfur atom of the thiophene ring with the central metal atom. Magnetic susceptibility data and electronic and ESR spectra suggest a distorted octahedral structure for the Ni(II) complex and tetrahedral geometry for the Zn(II) complex. The Schiff base and its metal chelates were screened for in-vitro activity against four bacteria, two Gram-positive (Bacillus subtilis and Staphylococcus aureus) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa), and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to have greater antibacterial activity than the free Schiff-base chelate.     

New Regional Editor

The complexes Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 3-(anilinomethylene)-2-methoxychroman-4-one were synthesized and characterized by elemental analysis, conductivity, infrared and UV?CVis spectroscopy, ¹H NMR, X-ray diffraction patterns, magnetic susceptibility and thermal analysis (TG/DTG/DSC). The X-ray analysis shows that the studied compounds crystallize in the triclinic crystal system and they are no isostructural complexes. The unit cell parameters for these chelates were presented. The molecules of solvent are in the outside coordination sphere of the complexes. The chelates have different thermal stability and they decompose in air atmosphere in three steps. The coordination of metal ions is through nitrogen atom from ligand and oxygen atom present in 4-position of ??-pyrone. The studied chelates have electrolyte (1:1) and non-electrolyte nature. They are high-spin complexes with octahedral coordination and the weak ligand fields.     

Coordination Behavior of N‐Donor Schiff Base Derived from 2‐Benzoylpyridine Toward Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), and Cr(III) Metal Ions: Synthesis,Spectroscopic and Thermal Studies,and Biological Activity

A new Schiff base was prepared from the reaction of 4,4′‐methylenedianiline with 2‐benzoylpyridine in 1:2 molar ratio, as well as its different metal chelates. The structures of the ligand and its metal complexes were studied by elemental analyses, spectroscopic methods (infrared [IR ], ultraviolet–visible [UV –vis], ¹H nuclear magnetic resonance [NMR ], electron spin resonance [ESR ]), magnetic moment measurements, and thermal studies. The ligand acts as tetradentate moiety in all complexes. Octahedral geometry was suggested for Mn(II ), Cu(II ), Cr(III ), and Zn(II ) chloride complexes and pentacoordinated structure and square planar geometry for Co(II ), Ni(II ), Cu(NO₃ )₂, CuBr₂ , and Pd(II ) complexes. ESR spectra of copper(II ) complexes ( 4 )–( 6 ) at room temperature display rhombic symmetry for complex ( 4 ) and axial type symmetry for complexes ( 5 ) and ( 6 ), indicating ground state for Cu(II ) complexes. The derivative thermogravimetric (DTG ) curves of the ligand and its metal complexes were analyzed by using the rate equation to calculate the thermodynamic and kinetic parameters, which indicated strong binding of the ligand with the metal ion in some complexes. Also, some of these compounds were screened to establish their potential as anticancer agents against the human hepatic cell line Hep‐G₂ . The obtained IC₅₀ value of the copper(II ) bromide complex (4.34 µg/mL ) is the highest among the compounds studied.     

Antimicrobial activity of aniline‐formaldehyde resin modified by adding piperazine moiety and its metal polychelates

Aniline‐formaldehyde resin modified by adding piperazine (AFP) was prepared in alkaline medium, and its metal polychelates have also been prepared with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) metal ions. The synthesized compounds were characterized by elemental, spectral (UV–Vis, IR, ¹H‐NMR and ¹³C‐NMR), thermogravimetric analysis (TGA), and magnetic moment measurements. The percentage of metal in all of the polychelates was found to be consistent with 1:1 (metal/resin) stoichiometry. The thermal behaviors of these coordination polymers were studied by TGA in a nitrogen atmosphere up to 750°C. The TGA results revealed that all the metal polychelates had higher thermal‐resistance property compared to the common resin (AFP). The magnetic moment measurements and UV–Vis spectra confirmed the geometry of the central metal ion in all the polychelates. All the synthesized metal polychelates showed excellent antibacterial activities against the selected bacteria. The antibacterial activities were determined using the shaking flask method, where 25 mg/ml concentrations of each compound were tested against 10⁵ CFU/ml bacteria solutions. The number of viable bacteria was calculated by using the spread plate method, where 100 µl of the incubated antibacterial agent in bacteria solutions was spread on agar plates, and the number of bacteria was counted after 24 hr of incubation period at 37°C. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and Thermal Investigation of Some Metal Complexes Containing Polydentate ONO-Donor Heterocyclic Schiff Base Ligand

Cu(II), Co(II), Ni(II), and Zn(II) metal complexes with new heterocyclic Schiff base derived from 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one and 3-methoxysalicylaldehyde have been synthesized and characterized on the basis of elemental analyses, electronic, IR, and ¹H NMR spectra, and also by aid of molar conductivity measurements, magnetic moment measurements, and thermogravimetric analyses. It has been found that the Schiff base behaves as a neutral bidentate (NO) and tridentate (ONO) ligand forming chelates with 1 : 2 (metal : ligand) stoichiometry. Octahedral configuration is suggested for metal complexes. The conductivity data for the Ni(II) complexes are consistent with those expected for a 1 : 2 electrolyte.     

Transition metal polymeric chelates: Spectral, magnetic, thermal behaviour of polymeric chelates of poly(resacetophenone diyl ethylene)s with Ni(II), Cu(II), Mn(II), Zn(II) and Co(II)

Polymeric chelates of the type [ML₂]_n where M = Ni(II), Cu(II), Zn(II) or Co(II), L = poly(resacetophenone diyl ethylene)s, andn= degree of polymerization, have been synthesized. Their structures have been elucidated on the basis of analytical, magnetic, electronic and IR spectral studies. Electronic spectra in conjunction with magnetic moments are in accord with an octahedral environment around the central metal ion in all polymeric chelates except Cu(II) and Zn(II) polymeric chelates which have been shown to possess square planar and tetrahedral geometries, respectively. IR spectral studies further suggest that the metal ions are coordinated through the oxygens of the carbonyl and the phenolic hydroxyl groups. All the chelates are paramagnetic except Zn(II), which is found to be diamagnetic.     

Coordination polymer with a staircase molecular architecture: Connecting binuclear Zn(II) bis-chelate platforms with bridging 4,4′-bipyridyl

A new tetraketone ligand with two separated β-diketone functions was prepared, 1,3-[CO-CH₂-COC(CH₃)₂OCH₃]₂Ph (H₂L ^iPrOMe). The title coordination polymer, [Zn₂(L ^iPrOMe)₂(DMSO)₂(bipy)]_n (DMSO = dimethylsulfoxide; bipy = 4,4′-bipyridyl), formed as the only crystalline product upon interaction of Zn(II) acetate, H₂L ^iPrOMe and bipy in 1:1:1 to 1:1:5 molar ratios in DMSO as a solvent. A single crystal XRD study of the compound revealed a staircase polymeric architecture of the complex. The architecture is based on binuclear ′Zn₂(L ^iPrOMe)_2′ platforms where each Zn(II) cation is chelated by two β-diketonate groups of two L ^iPrOMe ligands in the equatorial plane, while each L ^iPrOMe ligand chelates two Zn(II) cations. The coordination environment of each Zn(II) is completed to a distorted octahedron by an O atom of a terminal DMSO and an N atom of bridging bipy ligands. The resulting staircase polymeric ribbons are packed in a self-inclusion mode as would be expected for van der Waals interactions. Most fragments of the molecule were found to be disordered over two equally populated orientations, which was interpreted as evidence of a modulated structure. In addition, several fragments reveal additional minor disordering and high thermal motion.     

Synthesis,characterization, electrical conductivity,and catalytic studies of some coordination polymers of salen-type schiff base

Coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) with the salen-type Schiff base 4,4′-bis[(N-ethanesalicylaldehydediamine-5)azo]biphenyl have been prepared and characterized by elemental analyses, IR and electronic spectra, magnetic susceptibility measurements, and thermogravimetric analysis. Thermogravimetric analysis confirms the coordination of H₂O in complexes. The ¹H NMR spectrum of ligand clearly indicates the presence of OH and azomethine groups. The octahedral geometry have been suggested for Mn(II), Fe(II), Co(II), and Ni(II) complexes, and square planar Cu((II), whereas tetrahedral is suggested for Zn(II) and Cd(II) polychelates. Thermal data have been analyzed for kinetic parameters by both Coat-Redfern and Broido methods. Solid-state dc conductivity of ligand and its polychelates was measured in their compressed pellet form over 313–413 K temperature range. Solidstate conductivity lies in the range 4.361 × 10⁻¹¹ to 7.241 × 10⁻¹⁰ Ohm⁻¹ cm⁻¹ indicating their semiconducting behavior. Oxidation of styrene with selected catalysts was tested using H₂O₂ as an oxidant.     

Synthesis and spectroscopic studies of some transition metal complexes of a novel Schiff base ligands derived from 5-phenylazo-salicyladehyde and o-amino benzoic acid

Cu(II), Mn(II), Ni(II), and Zn(II) metal complexes with novel heterocyclic Schiff base derived from 5-phenyl azo-salicyladehyde and o-amino benzoic acid have been synthesized and characterized on the basis of elemental analyses, electronic, IR, and (1)H NMR spectra, and also by aid of scanning electron microscopy (SEM), X-ray powder diffraction, molar ratio measurements, molar conductivity measurements, and thermogravimetric analyses. It has been found that the Schiff base behaves as neutral tridentate (ONO) ligand forming chelates with 1:1 (metal:ligand) stoichiometry.