Aromatic Interactions: Frontiers in Knowledge and Application
CHAPTER 5: Solution-Phase Measurements of Aromatic Interactions
Published:15 Nov 2016
K. D. Shimizu, P. Li, J. Hwang, 2016. "Solution-Phase Measurements of Aromatic Interactions", Aromatic Interactions: Frontiers in Knowledge and Application, Darren W Johnson, Fraser Hof
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The non-covalent interactions of aromatic surfaces are important components of many chemical and biological solution-based processes.1–9 Examples include: reaction selectivity and catalysis,10–18 supramolecular assembly,19–22 drug–protein interactions,23 and structure and function of biomacromolecules.24–30 Theoretical models of these interactions provide some guidance in predicting their relative strengths and stability trends.31–48 However, the accuracy of these calculations is still limited due to their relatively weak interaction energies and the complexity of their contributing terms.49–53 The non-covalent interactions of aromatic surfaces, unlike hydrogen bonds, dipole–dipole, or electrostatic interactions, are not dominated by the electrostatic term. Instead, aromatic interactions are typically made up of multiple contributing terms of similar magnitude such as electrostatic, dispersion, repulsion, and solvent effects. The dispersion and solvent terms are particularly challenging, as methods to accurately model them are still being developed. Thus, the accurate experimental measurements of the strengths and stability trends for aromatic interactions in solution have significant value in aiding the development of fundamental models and in guiding the design of practical applications of these interactions. The goal of this chapter is to provide a tutorial review of current experimental studies of aromatic interactions in the solution phase. Illustrative systems from the literature were selected to provide practical examples on how different experimental strategies can be used to measure and analyze these weak non-covalent interactions and to highlight advantages and disadvantages of each approach.