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Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

100%
Kaczmarzyk T., Rutkowska I., Dziliński K.
Nukleonika
|
2015
|
vol. 60
|
issue 1
51-55
EN
Molecular and electronic structure changes during successive reduction of a Fe-tetraphenylporphyrin chloride [Fe(III)(TPP):Cl] complex are reported on the basis of Mössbauer spectroscopy and DFT calculations. It is established that the attachment of additional electrons to a neutral Fe(III)(TPP):Cl molecule leads to significant shortening of Fe-N distances at the first stage of the reduction Fe(III)(TPP):Cl → Fe(II)(TPP) and lengthening of these bonds at the second stage Fe(II)(TPP) → Fe(I)(TPP). Changes of other bond lengths of the porphyrin ring also appear but in less degree. Interaction of Fe(II) and Fe(I)(TPP) with tetrahydrofuran (THF) solvent is considered. Electron configuration of Fe(II)(TPP) corresponds to intermediate-spin (S = 1) state and in the case of Fe(I)(TPP) low-spin state (S = ½) is observed. Electron density distribution in Fe(II)- and Fe(I)(TPP) complexes, in association with Mössbauer data, is analyzed. Good correlation between experimental and theoretical results was obtained.
2
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Mössbauer study of a tetrakis (pentafluorophenyl) porphyrin iron (III) chloride in comparison with the fluorine unsubstituted analogue

100%
Kaczmarzyk T., Dziedzic-Kocurek K., Rutkowska I., Dziliński K.
Nukleonika
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2015
|
vol. 60
|
issue 1
57-61
EN
Mössbauer investigations, in association with density functional theory (DFT) calculations, have been conducted for the molecular and electronic structures of iron (III) [tetrakis (pentafluorophenyl)] porphyrin chloride [(F20TPP)Fe:Cl], as a Fe(III)-tetraphenylporphyrin complex containing chloride axial ligand and substituted hydrogen atoms by fluorine ones in the four phenyl rings, in comparison with its fluorine unsubstituted analogue [(TPP)Fe:Cl]. It was found that the parameters of Mössbauer spectra of both complexes are close to one another, and correspond to the high-spin state of Fe(III) ions, but they show the different temperature dependence and the quadrupole doublets in Mössbauer spectra show different asymmetry at low temperatures. Results of DFT calculations are analyzed in the light of catalytic activity of the halogenated complex.
3
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The microstructure and magnetic properties of Nd8.5Tb1.5Fe83Zr1B6ribbons obtained at various cooling rates

88%
Dośpiał M., Olszewski J., Nabiałek M., Pietrusiewicz P., Kaczmarzyk T.
Nukleonika
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2015
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vol. 60
|
issue 1
15-18
EN
The paper presents results of microstructure and magnetic properties studies of Nd8.5Tb1.5Fe83Zr1B6 ribbons obtained by melt-spinning technique. The samples were produced using the rapid cooling of liquid alloy on the copper wheel, by applying three different linear velocities 20, 30, and 35 m/s. The microstructure of obtained ribbons was examined using X-ray diffractometry and Mössbauer spectroscopy. Magnetic measurements were performed using LakeShore vibrating sample magnetometer. The microstructure measurements were used for quantitative and qualitative analysis of phase composition. Basing on results of structure studies combined with magnetic measurements, the influence of phase composition on hysteresis loop behavior was described.
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