Synthesis, characterization, and properties of polychelates of poly(maleic acid-co-olefin) with Cu(II), Co(II), Ni(II), and Zn(II)

SUMMARY Polychelates of poly(maleic acid-co-olefin) with Cu(II), Co(II), Ni(II), and Zn(II) metal ions are synthesized. These compounds are characterized by FT IR, UV-vis spectroscopy, and thermal analysis. The electrical conductivity measurements are carried out. These demonstrate that at temperature close to 130°C the electrical conductivity increased to values near to the semiconductor range. The PM3 calculations are also carried to study the geometry of the polychelates. Received: 1 November 2000/Revised version: 20 March 2001/Accepted: 21 March 2001     

Polychelates of poly(acrylic acid-co-acrylamide)with Cu(II), Co(II), and Ni(II) Synthesis and properties

SUMMARY Polychelates were obtained by addition of an aqueous solution of the poly(acrylic acid-co-acrylamide) to an aqueous solution of Cu(II), Co(II), and Ni(II). All the polychelates were insoluble in water and in common organic solvents. The polychelates were characterized by elemental analysis, FT-IR spectroscopy thermogravimetry, and showed tetrahedral arrangement for Co(II) and Ni(II). Magnetic and conductivity studies for all the polychelates were also carried out. The poly(acrylic acid-co-acrylamide) behaved as semiconductor. Received: 25 July 1997/Revised version: 1 December 1997/Accepted: 5 December 1997     

Synthesis and characterization of antibacterial polychelates of urea–formaldehyde resin with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) metal ions

We studied the reaction between urea and formaldehyde with the purpose of preparing new polychelates of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) metal ions. These compounds were characterized by elemental analysis, IR spectroscopy, ¹H‐NMR, electronic spectroscopy, thermogravimetric analysis (TGA), and molar conductance measurements. The percentage of metal in all of the polychelates was found to be consistent with 1:1.5 (metal/ligand) stoichiometry. The thermal behaviors of these coordination polymers were studied by TGA in a nitrogen atmosphere up to 750°C. The TGA results reveal that the complexes had higher thermal‐resistance properties compared to the common urea–formaldehyde resin. The molar conductivity and magnetic susceptibility measurements of the synthesized polychelates confirmed the geometry of the complexes. The antibacterial activity of the polychelates was also investigated with agar diffusion methods. The antibacterial activity of these polychelates was found to be reasonably good compared with standard drugs, namely, ciprofloxacin, ampicillin, and kanamycin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 928–936, 2006     

Synthesis,characterization, and properties of polychelates of poly(styrene sulfonic acid‐co‐maleic acid) with Co(II), Cu(II), Ni(II), and Zn(II)

Polymer metal complexes of poly(styrene sulfonic acid‐co‐maleic acid) and Cu(II), Ni(II), Co(II), and Zn(II) were synthesized. The magnetic, spectral, and thermal properties, as well as the electrical conductivities, of the chelates were investigated, and possible structures were assigned to the polychelates. Semiempirical calculations at the AM1 level were carried out on the geometrical arrangement of the polychelates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2546–2551, 2002     

Synthesis,characterization of poly(allylamine)chelates with Cu(II), Co(II) and Ni(II)

Summary The parent polymer, poly(allylamine) as ligand polymer was employed to synthesize polychelates of heavy metal ions. The functional poly(allylamine) and its Ni(II), Co(II) and Cu(II) metal chelates were characterized by elemental analysis, FT-IR spectroscopy, TGA, and SEM. For the polychelates magnetic and conductivimetry studies were also carried out.     

Synthesis and properties of chelate polymers of VO(II), Mn(II), Zn(II), Fe(III), and Cr(III) with schiff base of 5,5′-methylene bis-salicylaldehyde with aniline

Polychelates of VO(II), Mn(II), Zn(II), Fe(III), and Cr(III) were prepared from Schiff base of 5,5′-methylene bis-salicyladehyde with aniline. All the chelate polymers are amorphous and insoluble in common organic solvents. They have very little solubility in DMF. The first three polychelates are found to be noncharged chelate polymers while the last two polychelates are found to be ionic from their conductivities in DMF. Their probable structures were determined from reflectance electronic spectral and magnetic measurements in conjunction with infrared measurements. The thermal stability, order of reaction and activation energy for all the polychelates were determined from their thermogravimetric analyses.     

Studies on poly(2-hydroxy-4-acryloyloxybenzophenone)-metal complexes

2-Hydroxy-4-acryloyloxybenzophenone (HABP), prepared from acryloyl chloride with 2,4-dihydroxybenzophenone, was polymerized in methyl ethyl ketone at 70°C using benzoyl peroxide as initiator. Polychelates were obtained in the dimethylformamide solution of poly(HABP) containing a few drops of ammonia with the aqueous solution of Cu(II)/Ni(II) ions. The polymer and polychelates were characterized by elemental analyses and spectral studies. Elemental analyses of the polychelates suggest a metal to ligand ratio of 1:2. The IR spectral data of polychelates indicate that the metals were coordinated through the oxygen of the keto group and the oxygen of the phenolic-OH group. The diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moments of the polychelates show an octahedral and square planar structure for poly(HABP)-Ni(II) and poly(HABP)-Cu(II) complexes, respectively. X-ray diffraction studies revealed a high crystalline nature of the polychelates. The thermal properties of polymer and metal complexes and their catalytic activity are discussed. © 1996 John Wiley & Sons, Inc.     

Studies on various divalent metal complexes of poly(2-hydroxy-4-acryloyloxybenzophenone) in aqueous medium

2-Hydroxy-4-acryloyloxybenzophenone (2H4ABP) prepared by reacting acryloyl chloride with 2,4-dihydroxybenzophenone, was polymerized in 2-butanone at 65°C using benzoyl peroxide as initiator. Polychelates were obtained in the alkaline solution of poly(2H4ABP) with aqueous solutions of metal ions such as Ni(II), Mn(II), Co(II), Ca(II), Cd(II) and Zn(II). The polymer and polychelates were characterized by elemental analyses and spectral studies. Elemental analyses of the polychelates suggest that the metal-to-ligand ratio is 1: 2. The IR spectral data of the polychelates indicate that the metals were coordinated through the oxygen of the keto group and oxygen of the phenolic −OH group. The diffuse reflectance spectra, EPR and magnetic moments studies reveal that the polychelates of Cu(II) complex are square planar, and Ni(II), Mn(II) and Co(II) complexes are octahedral, while Ca(II), Cd(II) and Zn(II) complexes are tetrahedral. X-ray diffraction studies revealed that the polychelates are highly crystalline. The thermal and electrical properties of polymer and polymer–metal complexes are discussed. © 1998 SCI.     

New polymeric Schiff base and its metal complexes

A novel polymeric Schiff base was synthesized by the reaction of a Schiff base from 2,4‐dihydroxy benzaldehyde and aniline with acryloyl chloride and was polymerized in methyl ethyl ketone at 70°C with benzoyl peroxide as a free‐radical initiator. Polychelates were obtained in an alkaline solution of poly(2‐hydroxy‐4‐acryloyloxy‐N‐phenylbenzylidine) with aqueous solutions of metal ions such as Cu(II), Ni(II), Co(II), Ca(II), Cd(II), Mn(II), and Zn(II). The polymeric Schiff base and polychelates were characterized with elemental analysis and spectral studies. The elemental analysis of the polychelates suggested that the metal‐to‐ligand ratio was 1:2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polychelates of the Cu(II) complex were square‐planar, those of the Ni(II), Mn(II), and Co(II) complexes were octahedral, and those of the Ca(II), Cd(II), and Zn(II) complexes were tetrahedral. X‐ray diffraction studies revealed that the polychelates were highly crystalline. The thermal properties of the Schiff base and polychelates were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 494–500, 2004     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Coordination polymers,VII. Polymeric metallated organic pigments of the schiff base derived from 4,4′-(4,4′-biphenylylene bisazo)di(salicylaldehyde) and p-toluidine

Chelate polymers of Cr(III), Fe(III), Fe(II), Co(II), Ni(II), and Cu(II) with the schiff base of 4,4′-(4,4′-biphenylylene bisazo)di(salicylaldehyde) with p-toluidine have been prepared. All the polychelates are dark coloured and insoluble in common organic solvents. The octahedral structures of the polychelates were suggested on the basis of electronic spectra and magnetic susceptibility measurements in conjunction with infra-red measurements. All polychelates are non-electrolytes. The thermal stability of all the polychelates was determined from their thermogravimetric analyses.     

Studies on poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) and its metal complexes

8‐Hydroxy‐4‐azoquinolinephenylmethacrylate (8H4AQPMA) was prepared and polymerized in ethyl methyl ketone (EMK) at 65°C using benzoyl peroxide as free radical initiator. Poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) poly(8H4AQPMA) was characterized by infrared and nuclear magnetic resonance techniques. The molecular weight of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) complexes of poly(8H4AQPMA) were prepared. Elemental analysis of polychelates suggests that the metal‐ligand ratio is about 1 : 2. The polychelates were further characterized by infrared spectra, X‐ray diffraction, spectral studies, and magnetic moments. Thermal analyses of the polymer and polychelates were carried out in air. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1516–1522, 2006     

Poly(styrene‐alt‐maleic acid)–metal complexes with divalent metal ions. synthesis,characterization, and physical properties

Polymer–metal complexes of the alternating copolymer styrene and maleic acid with Cu(II), Co(II), Ni(II), and Zn(II) were synthesized and characterized by elemental analysis, infrarred and electronic spectra, and thermogravimetry. In addition, magnetic measurements were performed and the electrical conductivity was studied at different temperatures. Semiempirical calculations at the PM 3 level were carried out to elucidate the geometrical arrangement of the polychelates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1310–1315, 2001     

Mn(II), Co(II) and Ni(II) complexes of 4-(2-thiazolylazo)resorcinol: Syntheses, characterization, catalase-like activity, thermal and electrochemical behaviour

Manganese(II), cobalt(II) and nickel(II) acetates react with the ligand, 4-(2-thiazolylazo)resorcinol, to form complexes of general formula [ML₂] for MCo(II), Ni(II) and [ML₂]·2H₂O for MMn(II). Each of the azo complexes was characterized using elemental analysis, electrolytic conductance, UV–visible spectroscopy and magnetic susceptibility. An octahedral structure is proposed for all complexes prepared, which molar conductance data revealed to be non-electrolytes. IR spectra reveal that the ligand is coordinated to the metal ions in a tridentate manner via the resorcinol OH, azo N and thiazole N groups as donor sites. The electrochemical behaviour of the ligand and its complexes were obtained by cyclic voltammetry. Thermal decomposition studies were undertaken to secure additional information on the structure of the investigated compounds. The manganese(II) complex catalysed the disproportionation of hydrogen peroxide in the presence of imidazole.     

Synthesis and properties of chelate polymers of Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) with a schiff's base of 5,5′-methylene-bis(3,3′-dinitrosalicylaldehyde) with 1,6-hexanediamine

The synthesis, characterization and coordination aspects of the title polymer ligands are reported. The polymeric chelates were prepared by polycondensations of transition metal ions (M) with a poly(Schiff's base) (L). The analytical data propose a (ML)_n formula for the chelates. All the polychelates are stable and insoluble in common organic solvents. The geometry around the central metal ion in each chelate is proposed on the basis of measurements of magnetic susceptibilities and UV reflectance spectra. The ligand field splitting parameters 10 Dq, the interelectronic repulsion parameter B, the nephelauxetric parameter β and ligand field splitting energies (L.F.S.E.) have been calculated for Ni(II) and Co(II) chelates. All chelates are resistant to moderately concentrated acids and dilute alkalies at ambient temperature. They exhibit thermal stabilities to varying degrees. IR spectra show that the ligand usually coordinates via the carbonyl oxygen (C=O) and the phenolic OH with replacement of hydrogen by metal ions.     

Synthesis,characterization and antimicrobial activity of transition metal chelated thiourea‐formaldehyde resin

A polymeric ligand (thiourea‐formaldehyde resin ‐ TUFR) bearing nitrogen and sulfur donor groups was synthesized by the polycondensation of thiourea and formaldehyde in acidic medium and its polychelates were prepared in alcoholic solution of metal ions such as Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). The TUFR polymeric ligand and its TUFR‐M(II) polychelates were characterized with micro‐analytical analysis and spectral studies. The FTIR spectra of polychelates indicated that the metal ions were coordinated through the sulfur of the thionyl (C?S) groups and formed a covalent bond with the nitrogen of the NH groups. Electronic spectra, electronic spin resonance (ESR) spectra and magnetic moments revealed that the polychelates of Mn(II), Co(II) and Ni(II) were octahedral; however, Cu(II) and Zn(II) polychelates were square‐planar and tetrahedral, respectively. The thermogravimetric analysis data indicated that the polychelates were more stable than the corresponding ligand. The antimicrobial activities of all the compounds against several bacteria and fungi were also investigated by using the agar well diffusion method. Copyright © 2006 Society of Chemical Industry     

Polychelates of poly[N-(4-carboxy-3-hydroxyphenyl)maleimide]

The reactions of the bidentate polymeric chelating ligand poly[N-(4-carboxy-3-hydroxyphenyl)maleimide] with Co(II), Ni(II), Cu(II), Zn(II) and UO₂(II) metal ions were investigated. Analytical, magnetic, spectral and thermal studies were used to characterize these polychelates. All these polychelates are stable, intensely coloured solids and insoluble in common organic solvents.     

Synthesis and some properties of PVC-bound dimethylglyoxime complexes of Co(II), Ni(II), and Cu(II)

Poly(vinyl chloride) (PVC) has been reacted with dimethylglyoxime (DMG) in THF to form the PVC–DMG comples, which has been characterized by spectroscopic and elemental analyses. The latter indicate that there is one DMG moiety anchored on the PVC chain by displacing every 12th Cl atom in the chain. PVC–DMG has further been reacted with alcoholic solutions of Co(II), Ni(II), and Cu(II) to form the intensely colored PVC–DMG–M(II) complexes. The structures of these complexes have been analyzed by elemental and IR spectral analyses. The overall thermal stability of PVC–DMG–M(II) increases in the order: PVC < PVC–DMG–Cu(II) < PVC–DMG–Ni(II) < PVC–DMG–Co(II). The electrical conductivities are also significantly enhanced in the same order. The permittivities of these complexes are high relative to PVC at low frequency falling gradually with increasing frequency and the dielectric loss-frequency behavior is very broad.     

Polymer–metal complexes: Synthesis and characterization of poly(4-acetyl-3-hydroxyphenylacrylate) and its metal chelates

4-Acetyl-3-hydroxyphenylacrylate (AHAH) was synthesized and polymerized in 2-butanone using benzoyl peroxide as initiator. Poly(4-acetyl-3-hydroxyphenyl-acrylate) (PAHAH) was characterized by infrared and nuclear magnetic resonance techniques. The molecular weight of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) chelates of PAHAH were synthesized. The diffuse reflectance spectra and magnetic moments of the polychelates show distorted planar and octahedral structures for poly[Ni(AHA)₂] and poly[Cu(AHA)₂(OH₂)₂] complexes, respectively. The thermal properties of the polychelates are also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 177–182, 1998     

Synthesis and characterization of alumina-supported Mn(II), Co(II), Ni(II) and Cu(II) complexes of bis(salicylaldiminato)hydrazone as catalysts for oxidation of cyclohexene with tert-buthylhydroperoxide

Complexes of type [M(SAH)(OH₂)], where M is Mn(II),Co(II),Ni(II) and Cu(II), and SAH is the Schiff-base formed by condensation of salicylaldehyde (2 equiv.) and hydrazine (1 equiv.), bis(salicylaldiminato)hydrazone, or “2-({(z)-2-[(E)-1-(2-hydroxyphenyl)methylidene]hydrazono}methyl)phenol” have been prepared and characterized by elemental analysis, IR, UV–vis spectroscopy, conductometric, small area X-ray photoelectron spectroscopy and magnetic measurements. Elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). The results indicate that the Schiff-base ligand coordinates through one azomethine nitrogen and two phenolic oxygen to the metal ions. Conductance measurements suggest the non-electrolytic nature of the complexes. The atomic concentration of the complexes showed the ratio of M:N:O = 1:2:3, that indicates that a water molecule was in the complex. Alumina-supported complexes “[M(SAH)OH₂]-Al₂O₃” catalyze the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). The major products of the reaction were 2-cyclohexene-1-ol, 2-cyclohexene-1-one and 2-cyclohexene-1-(tert-butylperoxy). The influence of solvent on the oxidation reaction has been studied. [M(SAH)OH₂]-Al₂O₃ shows significantly higher catalytic activity than other alumina-supported complexes. These catalysts can also be reused in the oxidation of cyclohexene several times. The new materials “[M(SAH)OH₂]-Al₂O₃” were characterized by several techniques: chemical analysis and spectroscopic methods (FT-IR, UV–vis, XRD, DRS).