Buckyplates and Buckybowls: Examining the Effects of Curvature on π-π Interactions

pi-pi interactions are integral to many areas of chemistry, biochemistry, and materials science. Here we use electronic structure theory to analyze how pi-pi interactions change as the pi-systems are curved in model complexes based on coronene and corannulene dimers. Curvature redistributes electronic charge in the pi-cloud and creates a dipole moment in these systems, leading to enhanced intermolecular electrostatic interactions in the concave-convex (nested) geometries that are the focus of this work. Curvature of both monomers also has a geometric effect on the interaction by decreasing the average C C distance between monomers and by increasing the magnitude of both favorable London dispersion interactions and unfavorable exchange-repulsion interactions. Overall, increasing curvature in nested pi-pi interactions leads to more favorable interaction energies regardless of the native state of the monomers, except at short distances where the most highly curved systems are less favorable as exchange repulsion terms begin to the interaction. dominate