Using Higher Fullerenes to Channel Halogen-Halogen Interactions

Fullerenes are fascinating to study in the solid state in regard to their supramolecular and host-guest chemistry. Through the utilization of single-crystal X-ray diffraction, the molecular and supramolecular structures of fullerenes can be determined. Much focus has been given to the host-guest nature of fullerenes in which the complementary molecules are often quite large and resemble the shape of the cage. Little focus, however, has been given to flat, smaller co-crystallization molecules. The molecules 1,2,4,5-tetrabromobenzene and hexabromobenzene were successfully co-crystallized with C₆₀, C₇₀ and Sc₃N@I_h(7)-C₈₀ in order to study π-π interactions. While the C₆₀ structures show typical van der Waals interactions, the higher fullerenes show additional, unique halogen-halogen interactions.