Shape-persistent dehydrobenzannulenes (DBAs; also known as arylene ethynylene macrocycles, AEMs) of various geometries and sizes have been pursued as synthetic targets for more than half a century. 1 These π-conjugated macrocycles with conformationally rigid backbones and central cavities have been used in supramolecular chemistry and molecular recognition, host-guest chemistry, as components of organic sensors and organogels, nanoporous solids, 6a,6b and liquid crystals. Moore and coworkers' report that these π-conjugated macrocycles can form dimers and higher aggregates through [π•••π] interactions between the aromatic rings started attempts to modulate this aggregation by the installation of electron-donating, electron-withdrawing, or hydrogen bonding units onto the DBAs. As benzene and hexafluorobenzene [π•••π] stack in an electronically complementary and well-ordered alternating arrangement-a fact first recognized by Patrick and Prosser in 1960, and since studied in great detail -we speculated that their joint incorporation into the DBA structures could result in the formation of higher order columnar assemblies in the solid state.