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Substituent Effects in Parallel-Displaced π-π Stacking Interactions: Distance Matters.

  • Riwar LJ Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
  • Trapp N Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
  • Kuhn B F. Hoffmann-La Roche Ltd., Pharma Research and Early Development (pRED), Therapeutic Modalities, Roche Innovation Center Basel, Grenzacherstrasse 124, 4070, Basel, Switzerland.
  • Diederich F Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
  • 2017-05-12
Published in:
  • Angewandte Chemie (International ed. in English). - 2017
Rebek imides
host-guest systems
substituent effects
supramolecular chemistry
π-π stacking interactions
English Host-guest systems with Rebek imide type receptors and a 2,6-di(isobutyramido)pyridine ligand were employed to investigate substituent effects in parallel-displaced π-π stacking interactions. Changing the intermolecular distance between the para substituent on the aromatic platform of the receptor and the pyridine ring of the guest results in a strongly different substituent effect. With a short ethyne-1,2-diyl spacer between the Rebek imide and the aromatic platform, partial overlap of substituent and guest stabilizes the π-π stacking interactions independent of the electronic nature of the substituent (Wheeler-Houk model). When the substituent is shifted further away by using a buta-1,3-diyne-1,4-diyl spacer, direct, through-space interactions between substituent and guest are prevented. A linear correlation between logKa (Ka =association constant) and the Hammett substituent constant σpara is observed, confirming predictions by the Hunter-Sanders model experimentally.
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  • English
Open access status
bronze
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https://folia.unifr.ch/global/documents/202673
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