Document Detail

Towards a More Complete Understanding of Non-Covalent Interactions Involving Aromatic Rings.
MedLine Citation:
PMID:  24937084     Owner:  NLM     Status:  Publisher    
Non-covalent interactions involving aromatic rings, which include π-stacking interactions, anion-π interactions, and XH/π interactions, among others, are ubiquitous in chemical and biochemical systems. There have been dramatic advances in our understanding of these interactions over the last decade. Despite these efforts, many aspects of these non-covalent interactions have only recently been uncovered, with many questions remaining. We summarize our computational studies aimed at understanding the impact of substituents and heteroatoms on these non-covalent interactions. In particular, we discuss our local, direct interaction model of substituent effects in π-stacking interactions. In this model, substituent effects are dominated by electrostatic interactions of the local dipoles associated with the substituents and the electric field of the other ring. The implications of the local nature of substituent effects on π-stacking interactions in larger systems are discussed, with examples given for complexes with carbon nanotubes and a small graphene model, as well as model stacked discotic systems. We also discuss related issues involving the interpretation of electrostatic potential (ESP) maps. Although ESP maps are widely used in discussions of non-covalent interactions, they are often misinterpreted. Next, we provide an alternative explanation for the origin of anion-π interactions involving substituted benzenes and N-heterocycles, and show that these interactions are well-described by simple models based solely on charge-dipole interactions. Finally, we summarize our recent work on the physical nature of substituent effects in XH/π interactions. Together, these results paint a more complete picture of non-covalent interactions involving aromatic rings, and provide a firm conceptual foundation for the rational exploitation of these interactions in a myriad of chemical contexts.
Steven E Wheeler; Jacob W G Bloom
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2014-6-17
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  -     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2014 Jun 
Date Detail:
Created Date:  2014-6-17     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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