Substituent effects on aromatic stacking interactions

Scott L. Cockroft, Julie Perkins, Cristiano Zonta, Harry Adams, Sharon E. Spey, Caroline M.R. Low, Jeremy G. Vinter, Kevin R. Lawson, Christopher J. Urch, Christopher A. Hunter*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl3, and by comparison with the solid state structures of model compounds. The structural similarity of the complexes makes it possible to apply the double mutant cycle method to evaluate the magnitudes of 24 different aromatic stacking interactions. The major trends in the interaction energy can be rationalised using a simple model based on electrostatic interactions between the π-faces of the two aromatic rings. However, electrostatic interactions between the substituents of one ring and the π-face of the other make an additional contribution, due to the slight offset in the stacking geometry. This property makes aromatic stacking interactions particularly sensitive to changes in orientation as well as the nature and location of substituents.

Original languageEnglish
Pages (from-to)1062-1080
Number of pages19
JournalOrganic and Biomolecular Chemistry
Volume5
Issue number7
DOIs
Publication statusPublished - 2007

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