Crystal Engineering of Sterically Shielded Hexa

The crystal structures of four pentakis-tert-butyl hexa-peri-hexabenzocoronenes (HBCs), each with an additional sixth substituent namely iodide, methoxy, formyl, and nitro, are presented. We show that the additional substituent has a significant impact on the packing in the solid state and the data obtained can be utilised for crystal engineering. By introducing an electron accepting substituent it was possible to achieve columnar arrangements that were previously unknown for such highly tert-butylated HBCs. In this way we provide insight into the aggregation behaviour of nanographenes with sterically highly shielded edges.