Oligonuclear ferrocene amides : mixed-valent peptides and redox-switchable foldamers

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2011
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Siebler, Daniel
Gasi, Teuta
Carella, Luca M.
Förster, Christoph
Heinze, Katja
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Chemistry - A European Journal. 2011, 17(16), pp. 4540-4551. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201002101
Zusammenfassung

Trinuclear ferrocene tris-amides were synthesized from an Fmoc- or Boc-protected ferrocene amino acid, and hydrogen-bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X-ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α-helices composed of α-amino acids. Unlike ordinary α-amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono-, di-, and trications. Singly and doubly charged mixed-valent cations were probed experimentally by Vis/NIR, paramagnetic 1H NMR and Mössbauer spectroscopy and investigated theoretically by DFT calculations. According to the appearance of intervalence charge transfer (IVCT) bands in solution, the ferrocene/ferrocenium amides are described as Robin–Day class II mixed-valent systems. Mössbauer spectroscopy indicates trapped valences in the solid state. The secondary structure of trinuclear ferrocene tris-amides remains intact (coiled form) upon oxidation to mono- and dications according to DFT calculations, while oxidation to the trication should break the intramolecular hydrogen bonding and unfold the ferrocene peptide (uncoiled form).

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540 Chemie
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foldamers, iron, metallocenes, mixed-valent compounds, peptides
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ISO 690SIEBLER, Daniel, Michael LINSEIS, Teuta GASI, Luca M. CARELLA, Rainer F. WINTER, Christoph FÖRSTER, Katja HEINZE, 2011. Oligonuclear ferrocene amides : mixed-valent peptides and redox-switchable foldamers. In: Chemistry - A European Journal. 2011, 17(16), pp. 4540-4551. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201002101
BibTex
@article{Siebler2011-04-11Oligo-13939,
  year={2011},
  doi={10.1002/chem.201002101},
  title={Oligonuclear ferrocene amides : mixed-valent peptides and redox-switchable foldamers},
  number={16},
  volume={17},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={4540--4551},
  author={Siebler, Daniel and Linseis, Michael and Gasi, Teuta and Carella, Luca M. and Winter, Rainer F. and Förster, Christoph and Heinze, Katja}
}
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