The Diels-Alder reaction of tribenzohexadehydro[12]annulene (12) and 3,4-diphenyl-2,5-dimethylcyclopentadienone (13) at 300 degrees C gave the triple adduct 2,3,10,11,18,19-hexaphenyl-1,4,9,12,17,20-hexamethylhexa-o-phenylene (6b) in 13% yield. NMR and X-ray analysis indicated that 6b adopts a screw conformation (C2) rather than a crown conformation (C3), and computational studies seem to rule out any interconversion of the two. Palladium-catalyzed coupling of 1,2-bis(4-bromophenyl)-3,4,5,6-tetraphenylbenzene (17) and the corresponding bis(boronic acid) 18 gave a mixture of linear and cyclic oligomers of hexaphenylbenzene containing two to six hexaphenylbenzene subunits. A macrocyclic tetramer was isolated from this mixture in 5% yield, and X-ray analysis showed it to be the "supertetraphenylene" 7 (C168H112) that contains a large central cavity and packs to form highly solvated, porous crystals. The difficulties encountered in the purification of 7 led to the development of alternative, more highly selective syntheses that give the pure macrocycle more easily but in essentially the same overall yield.