Spontaneous Resolution of an Electron‐Deficient Tetrahedral Fe 4 L 4 cage

A highly electron‐deficient C 3 ‐symmetric tris(bipyridyl) ligand was prepared in four steps and used for the coordination of Fe(OTf) 2 , thereby resulting in the homochiral assembly of a new family of robust tetrahedral M 4 L 4 cages. This homochiral T‐symmetric cage containing a relatively large cavity of 330 Å 3 is capable of encapsulating an anionic guest, as was determined by mass spectrometry, 19 F NMR spectroscopy, and finally shown from its crystal structure. Moreover, crystallization of the cage from CH 3 CN led to crystals containing both (ΔΔΔΔ and ΛΛΛΛ) enantiomers, while crystallization from CH 3 OH resulted in crystals containing only the right‐handed (ΔΔΔΔ) cage. The difference in the crystal packing of the two crystal structures is discussed and a feasible explanation for the unique phenomenon among supramolecular cages—spontaneous resolution—is given.