<abstract xmlns="http://www.w3.org/1999/xhtml"><p>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.</p></abstract>

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.

Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

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{"article-title":"Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex"}

Molecular and electronic structure changes during successive reduction of a Fe-tetraphenylporphyrin chloride [Fe(III)(TPP):Cl] complex are reported on the...

Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

Publié en ligne: 12 mars 2015

Pages: 51 - 55

Reçu: 18 juin 2014

Accepté: 15 nov. 2014

DOI: https://doi.org/10.1515/nuka-2015-0014

Mots clés
DFT calculations, electronic structure, iron-(tetraphenyl)porphyrin, Mössbauer spectroscopy, reduction process

© Tomasz Kaczmarzyk, Iwona Rutkowska, Kazimierz Dziliński

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

Publié en ligne: 12 mars 2015

Pages: 51 - 55

Reçu: 18 juin 2014

Accepté: 15 nov. 2014

DOI: https://doi.org/10.1515/nuka-2015-0014

Mots clésDFT calculations, electronic structure, iron-(tetraphenyl)porphyrin, Mössbauer spectroscopy, reduction process

© Tomasz Kaczmarzyk, Iwona Rutkowska, Kazimierz Dziliński

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Mots clés
DFT calculations, electronic structure, iron-(tetraphenyl)porphyrin, Mössbauer spectroscopy, reduction process