Atropoisomeric aromatic cores enhance disorder inside the supramolecular packing of disk‐shaped mesogens. Core‐extension of perylene with an atropoisomeric [4]helicene fragment thus gives rise to a room‐temperature liquid crystal even with extremely short side chains. Replacement of diester moieties by imide substituents allows switching from donor‐ to acceptor‐type electronic characteristics.

With the aim of opening an efficient access to large and sterically crowded polycyclic arenes as well as improving insight into the geometrical preferences of the Scholl reaction, a versatile synthesis strategy has been developed to form a family of flexible yet strongly crowded substrates for multiple dehydrocyclizations. Their intramolecular Scholl reactions lead with high selectivity either to considerably twisted species where the initial C3 symmetry is maintained, or to strongly rearranged products where the formation of multiple [6]helicene fragments is avoided by the formation of unusual hexa[7]circulene moieties under loss of the C3 symmetry.