title: Can Dispersion Forces Govern Aromatic Stacking in an Organic Solvent?
abstract: Experimental support for the dominance of van der Waals dispersion forces in aromatic stacking interactions occurring in organic solution is surprisingly limited. The size-dependence of aromatic stacking in an organic solvent was examined. The interaction energy was found to vary by about 7.5 kJ mol(-1) on going from a phenyl-phenyl to an anthracene-pyrene stack. Strikingly, the experimental data were highly correlated with dispersion energies determined using symmetry-adapted perturbation theory (SAPT), while the induction, exchange, electrostatic, and solvation energy components correlated poorly. Both the experimental data and the SAPT-dispersion energies gave high-quality correlations with the change in solvent accessible area upon complexation. Thus, the size-dependence of aromatic stacking interactions is consistent with the dominance of van der Waals dispersion forces even in the presence of a competing polarizable solvent.
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
authors.forename: Lixu
authors.initials: L
authors.lastname: Yang
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
authors.forename: John B
authors.initials: JB
authors.lastname: Brazier
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Hubbard
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
authors.forename: David M
authors.initials: DM
authors.lastname: Rogers
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK. scott.cockroft@ed.ac.uk.
authors.forename: Scott L
authors.initials: SL
authors.lastname: Cockroft
keywords: aromatic interactions; molecular recognition; supramolecular chemistry