Four large, 6-fold symmetric, polyphenylene hydrocarbons have been prepared by short syntheses that chiefly employed alkyne trimerization, palladium-catalyzed coupling, and Diels-Alder reactions. The two largest of these molecules, hexakis [4'-(pentaphenylphenyl) biphenyl-4-yl] benzene (4, C294H198) and hexakis [4'-(2, 3, 4, 5-tetraphenylphenyl) biphenyl-4-yl] benzene (5, C258H174) are substructures of “phenylogous cubic graphite”, ...