An S-10-Symmetric 5-Fold Interlocked [2]Catenane

The reaction of sym-pentakis(4-aminothiophenyl)corannulene with 2-formyl-6-methylpyridine and Cu-I or 2-formyl-1,10-phenanthroline and M-II (M = Co, Zn) yields an S-10-symmetric 5-fold interlocked [2]catenane of two interpenetrating [(Cu5L2)-L-I](5+) cages or D-5-symmetric [(M5L2)-L-II](10+) cages, respectively. The new structures were characterized by X-ray crystallography, NMR spectroscopy, and mass spectrometry. Density functional theory computations point to dispersive energies on par with traditional covalent bond energies. Subcomponent exchange reactions favored formation of the [(Co5L2)-L-II](10+) cage over the [(Cu10L4)-L-I](10+) catenane. The single cage and catenane each cocrystallized with a corannulene guest to form a bowl-in-bowl substructure.