Shedding Light on the Nature of Host–Guest Interactions in PAHs-ExBox<sup>4+</sup> Complexes Glaucio R. Nagurniak Giovanni F. Caramori Renato L. T. Parreira Pedro A. S. Bergamo Gernot Frenking Alvaro Muñoz-Castro 10.1021/acs.jpcc.6b04844.s001 https://acs.figshare.com/articles/journal_contribution/Shedding_Light_on_the_Nature_of_Host_Guest_Interactions_in_PAHs-ExBox_sup_4_sup_Complexes/3473477 Host–guest (HG) systems formed by polycyclic aromatic hydrocarbons and ExBox<sup>4+</sup> are suitable models to gain a deeper understanding of π–π interactions, which are fundamental in supramolecular chemistry. The physical nature of HG interactions between ExBox<sup>4+</sup> (<b>1</b>) and polycyclic aromatic hydrocarbons (PAHs) (<b>2</b>-<b>12</b>) is investigated at the light of the energy decomposition (EDA-NOCV), noncovalent interactions (NCI), and magnetic response analyses. The EDA-NOCV results show that the dispersion forces play a crucial role in the HG interactions in PAHs⊂ExBox<sup>4+</sup> complexes. The HG interaction energies are dependent on both the size of the PAH employed and the number of π-electrons in the guest molecules. The parallel face-to-face arrangement between HG aromatic moieties is also fundamental to maximize the dispersion interaction and consequently for the attractive energy which leads to the inclusion complex formation. 2016-06-24 00:00:00 PAH HG interactions HG interaction energies NCI