“…In the supramolecular structures, one acenylene subunit is centered above the octadehydro [12] annulene moiety of the neighboring molecule, hinting at lessthan-ideal charge transport properties. Unlike the Hay-type dimers, 3 a-c 3 deviate from planarity -the (aza)acenylene subunits are slightly twisted with respect to each other, a feature also observed in Anthony's pentacene-based dehydroannulenes, [11,12] which is most likely a crystal packing effect as gas-phase structures were calculated to be planar. In contrast to the pentacene-based annulene exhibiting three-dimensional π-stacking interactions, only two-dimensional ones are observed in the trimers: In 3 a 3 (co-crystallyzing with chloroform) and 3 c 3 (solvent-free packing), two of the three "arms" overlap-distances between π-system distances amount to ~3.4 Å.…”