Oligonuclear ferrocene amides : mixed-valent peptides and redox-switchable foldamers
Oligonuclear ferrocene amides : mixed-valent peptides and redox-switchable foldamers
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Date
2011
Authors
Siebler, Daniel
Gasi, Teuta
Carella, Luca M.
Förster, Christoph
Heinze, Katja
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Chemistry - A European Journal ; 17 (2011), 16. - pp. 4540-4551. - ISSN 0947-6539. - eISSN 1521-3765
Abstract
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 Chemistry
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foldamers,iron,metallocenes,mixed-valent compounds,peptides
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SIEBLER, 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. 17(16), pp. 4540-4551. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201002101BibTex
@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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