A computational study of cation–π interactions in polycyclic systems: exploring the dependence on the curvature and electronic factors

Abstract

Density functional theory (B3LYP) calculations with double and triple-ζ quality basis sets were performed on the Li + and Na + π-complexes of corannulene 2 , sumanene 3CH 2 , heterosumanenes 3X , triphenylene 4 and heterotrindenes 5X . The metal ions bind to both convex and concave faces of buckybowls, with a consistent preference to bind to the convex surface by about 1–4 kcal/mol. The metal ion complexation with the π-framework of the central six-membered ring span wider range compared to benzene, indicating the control of size, curvature and electronic perturbations over the strength of cation–π interactions. Computations show that the bowl-to-bowl inversion barriers are only slightly altered upon metal complexation, indicating the continuity of bowl-to-bowl inversion despite metal complexation. We have calculated the binding energies of model systems, triphenylene ( 4 ) and heterotrindenes ( 5X ), which indicate that the interaction energies are controlled by electronic factors. While the inversion barrier is dependent mainly on the size of the heteroatom, the extent of binding is independent of the size of the atom or the bowl depth.