Polar Interactions between Stacked π Systems in Fluorinated 1,8‐Diarylnaphthalenes: Importance of Quadrupole Moments in Molecular Recognition

T-shaped arrangements in the homodimers A and C of benzene and hexafluorobenzene, respectively, are rationalized by polar effects, but face-to-face stacking dominates in the 1:1 heterodimer B. The dynamics of a series of fluorinated 1,8-diarylnaphthalenes clearly demonstrate the dependence of arene–arene interactions on the electronic characteristics of the arenes. The results are important for the design of supramolecular structures.