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Mössbauer spectra of two extended series of basic iron(III) carboxylates [Fe3O(O2CR)6(H2O)6]A (A− = ClO4 −, NO3 −)

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Abstract

Two series of basic iron(III) carboxylates [Fe3O(O2CR)6(H2O)3]A were prepared, with R = CCl3, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, (CH2)3Cl, Me, CHMe2, Et, CMe3. For the former series (1–12) A −  = ClO\(_{4}^{\,\,-}\) and for the latter (13–24) A −  = NO\(_{3}^{\,\,-}\). Complexes with R = CF3 were inaccessible for either counteranion, with all synthetic attempts leading to the butterfly complex [Fe4O2(O2CCF3)8 (H2O)6]. Crystal structures of 1, 2, 5, 7, 9–12, 14, 16, 21 and 23 revealed the close structural similarity of the complexes. Mössbauer studies revealed very similar isomer shifts for all complexes in the region of 0.51–0.54 mm s − 1, and variable quadrupole splittings, ranging from 0.36 to 0.76 mm s − 1. Mössbauer studies of the complexes were carried out in frozen MeCN solutions in order to assess their stability in solution. All complexes proved to be stable in MeCN solutions, except complex 13 (R = CCl3, A −  = NO\(_{3}^{\,\,-})\), which dissociated to a butterfly-type complex.

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Authors and Affiliations

  1. Institute of Materials Science, NCSR “Demokritos”, 153 10 Aghia Paraskevi, Attikis, Greece

    Anastasia N. Georgopoulou, Yiannis Sanakis, Vassilis Psycharis, Catherine P. Raptopoulou & Athanassios K. Boudalis

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  1. Anastasia N. Georgopoulou
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  2. Yiannis Sanakis
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  3. Vassilis Psycharis
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  4. Catherine P. Raptopoulou
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  5. Athanassios K. Boudalis
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Correspondence to Athanassios K. Boudalis.

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Georgopoulou, A.N., Sanakis, Y., Psycharis, V. et al. Mössbauer spectra of two extended series of basic iron(III) carboxylates [Fe3O(O2CR)6(H2O)6]A (A− = ClO4 −, NO3 −). Hyperfine Interact 198, 229–241 (2010). https://doi.org/10.1007/s10751-010-0179-2

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