Making Sense of Heteroatom Effects in π-π Interactions.

ABSTRACT: Heteroatoms can profoundly impact the strength and preferred geometry of parallel and T-shaped interactions between aromatic systems. Understanding these heteroatom effects is vital for the rational design of everything from pharmaceuticals to asymmetric catalysts and organic materials. We first examine how the introduction of N:, NH, and C═O groups changes the shape of the relaxed interaction energy curve for the parallel-displaced benzene dimer. These heteroatom effects are shown to be (1) additive; (2) dependent primarily on the orientation of the heteroatom(s) relative to the displacement axis; and (3) driven by electrostatic effects. We then introduce a simple conceptual model to make sense of these results based on the interaction of a local dipole associated with each heteroatom wit

SUBMITTER: Do KU 

PROVIDER: S-EPMC12412153 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature