To address the effects of molecular symmetry on the phase of columnar liquid crystals, a series of unsymmetry ( C 1 ) and symmetry ( D 3h ) hexa- peri -hexabenzocoronene derivatives was prepared. Compounds 3 and 4 , as well as a mixture of compounds 3 + 4 , all had a significantly lower melting temperature and clearing temperature than high-symmetry compounds ( D 6h ), and all results show a strong dependence on molecular symmetry.