Substituent Effects on Non-Covalent Interactions with Aromatic Rings: Insights from Computational Chemistry

Non‐covalent interactions with aromatic rings pervade modern chemical research. The strength and orientation of these interactions can be tuned and controlled through substituent effects. Computational studies of model complexes have provided a detailed understanding of the origin and nature of these substituent effects, and pinpointed flaws in entrenched models of these interactions in the literature. Here, we provide a brief review of efforts over the last decade to unravel the origin of substituent effects in π‐stacking, XH/π, and ion/π interactions through detailed computational studies. We highlight recent progress that has been made, while also uncovering areas where future studies are warranted. Bond of the rings: An overview of recent efforts to unravel the nature of substituent effects in non‐covalent interactions involving aromatic rings using computational chemistry is presented. These interactions include π‐stacking (see picture), XH/π, cation/π, and anion/π interactions.