Supramolecular cage encapsulation as a versatile tool for the experimental quantification of aromatic stacking interactions

Chemical Science
Carlo BravinCristiano Zonta

Abstract

The widespread presence of aromatic stacking interactions in chemical and biological systems, combined with their relatively small energetic contribution, have led to a plethora of theoretical and experimental studies for their quantification and rationalization. Typically, π-π aromatic interactions are studied as a function of substituents to gather information about the interaction mechanism. While experiments suggest that aromatic interactions are dominated by local electrostatic contacts between π-electron density and CH groups, theoretical work has raised the possibility that direct electrostatic interactions between local dipoles of the substituents may play a role. We describe a supramolecular cage that binds two aromatic carboxylates in a stacked geometry such that the aromatic substituents are remote in space. Chemical Double Mutant Cycles (DMCs) were used to measure fifteen different aromatic stacking interactions as a function of substituent (NMe2, OMe, Me, Cl and NO2). When both aromatic rings have electron-withdrawing nitro substituents, the interaction is attractive (-2.8 kJ mol-1) due to reduced π-electron repulsion. When both aromatic rings have electron-donating di-methylamino substituents, the interaction is r...Continue Reading

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Citations

May 11, 2019·Angewandte Chemie·Alan VanderkooyMáté Erdélyi
Jul 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Elena BadettiCristiano Zonta
Oct 16, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrea PintoLaura Rodríguez
Sep 16, 2020·ACS Applied Materials & Interfaces·Elena BadettiGiulia Licini
Jul 5, 2019·Journal of the American Chemical Society·Carlo BravinCristiano Zonta

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Methods Mentioned

BETA
NMR

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