Interaction between ions and substituted buckybowls: A comprehensive computational study

Complexes formed by substituted buckybowls derived from corannulene and sumanene with sodium cation or chloride anion have been computationally studied by using a variety of methods. Best results have been obtained with the SCS‐MP2 method extrapolated to basis set limit, which reproduces the highest‐level values obtained with the MP2.X method. All bowls form stable complexes with chloride anion, with stabilities ranging from ?6 kcal/mol in the methylated corannulene derivative to ?45 kcal/mol in the CN‐substituted sumanene. The opposite trend is observed in sodium complexes, going from deeply attractive complexes with the methylated derivatives (?36 kcal/mol with sumanene derivative) to slightly repulsive ones in the CN‐substituted bowls (2 kcal/mol in the corannulene derivative). Anion complexes are stabilized by large electrostatic interactions combined with smaller though significant dispersion and induction contributions. Conversely, cation complexes are stabilized by large induction contributions capable of holding together the bowl and the cation even in cases where the electrostatic interaction is repulsive. The effect of substitution is mainly reflected on changes in the molecular electrostatic potential of the bowl and, thus, in the electrostatic contribution to the interaction. Therefore, the variations in the stability of the complexes on substitution could be roughly predicted just considering the changes in the electrostatic interaction. However, other contributions also register changes mainly as a consequence of displacements on the position of the ion at the minimum, so the accurate prediction of the stability of this kind of complexes requires going further than the electrostatic approach. © 2014 Wiley Periodicals, Inc.