Electrostatics does not dictate the slip-stacked arrangement of aromatic π-π interactions.

Chemical Science
Kevin Carter-Fenk, John Herbert

Abstract

Benzene dimer has long been an archetype for π-stacking. According to the Hunter-Sanders model, quadrupolar electrostatics favors an edge-to-face CH⋯π geometry but competes with London dispersion that favors cofacial π-stacking, with a compromise "slip-stacked" structure emerging as the minimum-energy geometry. This model is based on classical electrostatics, however, and neglects charge penetration. A fully quantum-mechanical analysis, presented here, demonstrates that electrostatics actually exerts very little influence on the conformational landscape of (C6H6)2. Electrostatics also cannot explain the slip-stacked arrangement of C6H6⋯C6F6, where the sign of the quadrupolar interaction is reversed. Instead, the slip-stacked geometry emerges in both systems due to competition between dispersion and Pauli repulsion, with electrostatics as an ambivalent spectator. This revised interpretation helps to rationalize the persistence of offset π-stacking in larger polycyclic aromatic hydrocarbons and across the highly varied electrostatic environments that characterize π-π interactions in proteins.

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Citations

Jan 8, 2021·Chemical Communications : Chem Comm·Shogo AmemoriMotohiro Mizuno
Jan 28, 2021·The Journal of Physical Chemistry. a·John M Herbert, Kevin Carter-Fenk
Oct 28, 2020·Physical Chemistry Chemical Physics : PCCP·Kevin Carter-Fenk, John M Herbert
Jul 18, 2020·Physical Chemistry Chemical Physics : PCCP·Justin P JoyceAnthony K Rappè
Jun 3, 2021·The Journal of Organic Chemistry·Ga Young LeeEllen M Sletten
Jun 11, 2021·Inorganic Chemistry·Rushie Mae CedenoSareeya Bureekaew
Jul 25, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Evgenii Titov
Jul 20, 2021·ACS Omega·Aniket KunduG Naresh Patwari
Jul 22, 2021·Physical Chemistry Chemical Physics : PCCP·Wengan HeRuibo Wu
Aug 5, 2021·Chemistry : a European Journal·Lars RummelPeter R Schreiner
Aug 14, 2021·The Journal of Physical Chemistry. a·John M Herbert
Sep 3, 2021·The Journal of Chemical Physics·Evgeny EpifanovskyAnna I Krylov
Sep 23, 2021·Accounts of Chemical Research·Kevin Carter-FenkJohn M Herbert

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