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

[Image: see text] 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 [Cu(I)(5)L(2)](5+) cages or D(5)-symmetric [M(II)(5)L(2)](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 [Co(II)(5)L(2)](10+) cage over the [Cu(I)(10)L(4)](10+) catenane. The single cage and catenane each cocrystallized with a corannulene guest to form a bowl-in-bowl substructure.