Effects of silicon addition on the electrical and magnetic properties of copper-doped (La,Ca)MnO3 compounds

In this paper we report about the electrical properties of La 0.7Ca0.3MnO3 compounds substituted by copper on the manganese site and/or deliberately contaminated by SiO2 in the reactant mixture. Several phenomena have been observed and discussed. SiO2 addition leads to the formation of an apatite-like secondary phase that affects the electrical conduction through the percolation of the charge carriers. On the other hand, depending on the relative amounts of copper and silicon, the temperature dependence of the electrical resistivity can be noticeably modified: our results enable us to compare the effects of crystallographic vacancies on the A and B sites of the perovskite with the influence of the copper ions substituted on the manganese site. The most original result occurs for the compounds with a small ratio Si/Cu, which display double-peaked resistivity vs. temperature curves. © 2003 Elsevier B.V. All rights reserved.

Structures and physical properties of n=3 Ruddlesden-Popper compounds Ca4Mn3-xNbxO10 (0 <= x <= 0.2)

The Ruddlesden-Popper series of compounds Ca4Mn3-xNbxO10(x = 0-0.2) have been prepared by solid-state methods. Structural, magnetic, electrical, and magnetoresistive studies were performed on the compounds. Nb doping caused increases in both unit cell volume and octahedral distortion. The magnetization measurements indicated that the doped samples displayed ferromagnetism-like behavior, which could be explained by the double-exchange interaction between Mn4+ and Mn3+ induced by the charge-compensation effect.

MAGNETIC-PROPERTIES OF LANTHANUM MANGANITE AND VALENCE EQUILIBRIA OF MANGANESE

The paramagnetic susceptibility of lanthanum manganite has been measured over a wide temperature range (100-1073 K). On the basis of the thermodynamic equilibria between the various manganese ions with different valence and spin states and the magnetic interactions between the various manganese ions, a semiempirical formula has been proposed to calculate the paramagnetic susceptibilities of lanthanum manganite at different temperatures. The results indicate that most of the discrepancies between the calculated and experimental reciprocal susceptibilities of lanthanum manganite are less than 10% and that the relative contents of the various manganese ions in lanthanum manganite vary with temperature. The relative content of the trivalent manganese ion with a high spin state is dominant over the whole temperature range, while be relative content of the tetravalent manganese ion with a high spin state decreases monotonously with increasing temperature. At 300 K the calculated relative content of the tetravalent manganese ion in lanthanum manganite is about 34%, which is in good agreement with the experimental result (30%). There are some divalent manganese ions present in lanthanum manganite from low temperature to high temperature. The ratio of the relative contents of the tetravalent and divalent manganese ions in the compound varies with temperature. Above 750 K the relative content of the tetravalent manganese ion is less than that of the divalent manganese ion. The variation in the electrical resistivity of lanthanum manganite with temperature has also been interpreted reasonably.

Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Surface Properties and Catalytic Activity of Manganese Ferrospinels

In recent years considerable advances have been achieved in the study of the surface structure and mechanism of action of environmentally benign heterogeneous catalysts. The study entitled as surface properties and catalytic activity of manganese ferrospinels. In the present study we have prepared manganese ferrospinels of general formula Mn(1-x)BxFe2O4 via low temperature controlled co-precipation method. The study employed low temperature co-precipitation method for the preparation ofMn(1-x)BxFe2O4 specimens, where B is a metal cation such as Cr,Co, Ni,Cu and Zn. The catalytic activities of the systems were investigated for liquid-phase benzoylation of aromatic compounds and phenol hydroxylation and for vapour-phase reactions such as aniline alkylation, phenol methylation and ODH of ethylbenzene. The different series of manganese ferrites are proved to be excellent catalysts for various industrially important reactions such as Friedel-crafts benzoylation of aromatic compounds, methylation of aniline and phenol, hydroxylation of phenol and oxidative dehydrogenation of ethylbenzene. Due to the tightening of the environmental regulations, production of diphenols from phenol hydroxylation and reduction of phenolic pollutants in waste waters using these catalysts can be a promising approach because it demands only simple techniques and produce little environmental pollution.

Studies on metal complexes with acylhydrazones based on heterocyclic carbonyl compounds

Dept.of Applied Chemistry, Cochin University of Science and Technology

Syntheses, EPR spectral studies and crystal structures of manganese(II) complexes of neutral N,N donor bidentate Schiff bases and azide/thiocyanate as coligand

Four manganese(II) complexes Mn2(paa)2(N3)4 (1), [Mn(paa)2(NCS)2] 3/2H2O (2), Mn(papea)2(NCS)2 (3), [Mn(dpka)2(NCS)2] 1/2H2O(4) of three neutral N,N donor bidentate Schiff bases were synthesized and physico- chemically characterized by means of partial elemental analyses, electronic, infrared and EPR spectral studies. Compounds 3 and 4 were obtained as single crystals suitable for X-ray diffraction. Compound 4 recrystallized as Mn(dpka)2(NCS)2. Both the compounds crystallized in the monoclinic space groups P21 for 3 and C2/c for 4. Manganese(II) is found to be in a distorted octahedral geometry in both the monomeric complexes with thiocyanate anion as a terminal ligand coordinating through the nitrogen atom. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines and the zero field splitting parameters (D and E) were calculated.

Investigations into reactions involving manganese(IV) chemiluminescence

The reactivity and characterisation of solubilised manganese(IV) as a chemiluminescence reagent were systematically investigated. The analytical utility of this reagent was established for the determination of various alkaloids, pharmaceuticals and compounds of forensic interest. The methodology was then successfully applied to industrial process monitoring, clinical and illicit drug samples.

Susceptibility of Saccharomyces cerevisiae and lactic acid bacteria from the alcohol industry to several antimicrobial compounds

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermoanalytical study of the complexes of 4-dimetilaminocinnamylidenepiruvate with manganese (II), cobalt (II), nickel (II), cupper (II), zinc (II) and lead (II), in the solid state

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermoanalytical study of the complexes of 4-dimethylaminocynnamylidenepyruvate with manganese (II), cobalt (II), nickel (II), cupper (II), zinc (II) and lead (II), in the solid state

Solid state compounds M-4-DMCP, where 4-DMCP is 4-dimethylaminocynnamylidenepyruvate and M represents Mn (II), Co (II), Ni (II), Cu (II), Zn (II) and Pb (II) were prepared. These compounds were studied by thermoanalytical techniques: thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and complexometric titration with EDTA. From the results obtained by the complexometric titration with EDTA, TG, DTG and DSC curves, was possible to establish the hydration degree, stoichiometry and thermal stability of the prepared compounds.

Manganese Phthalocyanine as a Biomimetic Electrocatalyst for Phenols in the Development of an Amperometric Sensor

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Cation distribution and magnetic characterization of the multiferroic cobalt manganese Co2MnO4 spinel doped with bismuth

The structural and magnetic properties of the cubic spinel oxide Co 2MnO4 (Fd3m space group) doped with different concentrations of bismuth, were investigated by X-ray diffraction and SQUID magnetometry. The Bi3+ ions entering into the CoIII octahedral sites do not alter the effective moment, μeff ∼8.2 μB, whereas both the magnetization M50 kOe at the highest field (50 kOe) and the field-cooled MFC magnetizations increased when increasing the Bi content. The ferrimagnetic character of the parent compound, Co2MnO4, is maintained for all materials although the antiferromagnetic interactions Co2+-Co2+ are affected, resulting in higher values of the Curie-Weiss temperature. Due to the large ionic radius of Bi, octahedra distortions occur as well as valence fluctuations of the Mn ions, giving rise to Jahn-Teller effects and enhancing the exchange interactions. The off-center Bi3+ ion is responsible of non-centrosymmetric charge ordering and should lead to multiferroïsme conditions for the BixCo2-xMnO4 material. © 2012 Elsevier B.V.

Thermal behaviour of α-hydroxyisobutyric acid, sodium α-hydroxyisobutyrate and its compounds with some bivalent transition metal ions

Synthesis, characterization and thermal decomposition of bivalent transition metal α-hydroxyisobutyrates, M(C4H7O 3)2·nH2O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behaviour of α-hydroxyisobutyric acid and its sodium salt were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), infrared spectroscopy (FTIR), TG-DSC coupled to FTIR, elemental analysis and complexometry. All the compounds were obtained as dihydrated, except the copper one which was obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occurs in a single or two steps and the final residue up to 235 C (Mn), 300 C (Fe), 305 C (Co), 490 C (Ni), 260 C (Cu) and 430 C (Zn) is Mn2O3, Fe2O3, Co3O 4, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity and identification of the gaseous products evolved during the thermal decomposition of these compounds. Copyright © 2013 Published by Elsevier B.V. All rights reserved.

Manganese(II) complexes with thiosemicarbazones as potential anti-Mycobacterium tuberculosis agents

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)