Issue 7, 2015
From the journal:

Chemical Science

How important are dispersion interactions to the strength of aromatic stacking interactions in solution?†

Jungwun Hwang,a   Brent E. Dial,a   Ping Li,a   Michael E. Kozik,a   Mark D. Smitha  and  Ken D. Shimizu ORCID logo *a  

* Corresponding authors

a Department of Chemistry and Biochemistry, University of South Carolina, SC 29208, USA
E-mail: shimizu@mail.chem.sc.edu

Abstract

In this study, the contributions of London dispersion forces to the strength of aromatic stacking interactions in solution were experimentally assessed using a small molecule model system. A series of molecular torsion balances were designed to measure an intramolecular stacking interaction via a conformational equilibrium. To probe the importance of the dispersion term, the size and polarizability of one of the aromatic surfaces were systematically increased (benzene, naphthalene, phenanthrene, biphenyl, diphenylethene, and diphenylacetylene). After correcting for solvophobic, linker, and electrostatic substituent effects, the variations due to polarizability were found to be an order of magnitude smaller in solution than in comparison to analogous computational studies in vacuo. These results suggest that in solution the dispersion term is a small component of the aromatic stacking interaction in contrast to their dominant role in vacuo.

Graphical abstract: How important are dispersion interactions to the strength of aromatic stacking interactions in solution?

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Article information

DOI
https://doi.org/10.1039/C5SC01370D
Article type
Edge Article
Submitted
15 Apr 2015
Accepted
15 May 2015
First published
18 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 4358-4364

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How important are dispersion interactions to the strength of aromatic stacking interactions in solution?

J. Hwang, B. E. Dial, P. Li, M. E. Kozik, M. D. Smith and K. D. Shimizu, Chem. Sci., 2015, 6, 4358 DOI: 10.1039/C5SC01370D

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