A remarkable, regiospecific hydrogenation zips around the similar to4 nm perimeter of hexa-peri-hexabenzocoronenes (HBC) adding 18 hydrogen atoms, leading to the first peralkylated coronenes, in quantitative yields in some cases. Increasing steric bulk of side chains was found to hinder the reaction, while unsubstituted HBC could be converted to a modest extent despite its vanishing solubility. The structures of the novel coronenes are unequivocally confirmed by MALDI-TOF, H-1, C-13, and heteronuclear correlation NMR, and UV-vis absorption spectroscopy. The puckered-ring periphery of these discotics does not prohibit self-assembly to columnar structures in a fashion similar to that of the planar precursors, as determined from wide-angle X-ray diffraction, but decreases the isotropization temperature by similar to300 degreesC relative to the latter. Branching in the alkyl chains frustrates nucleation from the melt, resulting in clear polymorphism depending on the thermal treatment. Nonetheless, preliminary measurements indicate high charge-carrier mobilities and lifetimes within the bulk material, on the same order as those previously found for HBCs.