Spherical Supramolecular Structures Constructed via Chemically Symmetric Perylene Bisimides: Beyond Columnar Assembly

Abstract Like other discotic molecules, self‐assembled supramolecular structures of perylene bisimides (PBIs) are commonly limited to columnar or lamellar structures due to their distinct π‐conjugated scaffolds and unique rectangular shape of perylene cores. The discovery of PBIs with supramolecular structures beyond layers and columns may expand the scope of PBI‐based materials. A series of unconventional spherical packing phases in PBIs, including A15 phase, σ phase, dodecagonal quasicrystalline (DQC) phase, and body‐centered cubic (BCC) phase, is reported. A strategy involving functionalization of perylene core with several polyhedral oligomeric silsesquioxane (POSS) cages achieved spherical assemblies of PBIs, instead of columnar assemblies, due to the significantly increased steric hindrance at the periphery. This strategy may also be employed for the discovery of unconventional spherical assemblies in other related discotic molecules by the introduction of similar bulky functional groups at their periphery. An unusual inverse phase transition sequence from a BCC phase to a σ phase was observed by increasing annealing temperature.