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Noncovalent Forces pp 421–442Cite as

Unraveling the Origin of Substituents Effects in π-Stacking Interactions

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Part of the book series: Challenges and Advances in Computational Chemistry and Physics ((COCH,volume 19))

Abstract

Non-covalent interactions involving aromatic rings, which include π-stacking, anion-π, and cation-π interactions, among others, are central to modern chemical research. These interactions play vital roles in everything from protein-DNA interactions and the properties of organic electronic materials to stereoselective organocatalyzed reactions. We discuss recent efforts to understand the impact of substituents on the strength of π-stacking interactions through the application of modern tools of computational quantum chemistry. We first provide an account of previous efforts to develop qualitative physical models of these interactions, followed by apparent flaws in these previous models. We then present our local, direct interaction model of substituent effects in π-stacking interactions, and discuss recent extensions of this model based on the examination of electric fields of arenes. We also discuss related misconceptions regarding molecular electrostatic potentials (ESPs), and offer a simpler view of the origin of ESP differences arising from the incorporation of heteroatoms or substituents into aromatic rings. Finally, we conclude with an outlook for future advances in our understanding of π-stacking interactions.

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Acknowledgment

This work was supported by the National Science Foundation (Grant CHE-1254897) and the Welch Foundation (Grant A-1776). We also thank the Texas A&M Supercomputing Center for providing computational resources and J. W. G. Bloom, R. K. Raju, K. N. Houk, D. A. Dougherty, C. Corminboeuf, H. M. Jaeger, F. A. Evangelista, B. L. Iverson, and J. S. Siegel for many fruitful discussions about π-stacking interactions.

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  1. Department of Chemistry, Texas A&M University, 77843, College Station, TX, USA

    Steven E. Wheeler

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  1. Steven E. Wheeler
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  1. Department of Chemistry & Biochemistry, Utah State University, Logan, Utah, USA

    Steve Scheiner

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Wheeler, S. (2015). Unraveling the Origin of Substituents Effects in π-Stacking Interactions. In: Scheiner, S. (eds) Noncovalent Forces. Challenges and Advances in Computational Chemistry and Physics, vol 19. Springer, Cham. https://doi.org/10.1007/978-3-319-14163-3_14

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