6533b85bfe1ef96bd12baa7a

RESEARCH PRODUCT

Spontaneous Resolution of an Electron‐Deficient Tetrahedral Fe4L4cage

Pia BonakdarzadehKari RissanenFangfang PanElina KaleniusOndřej Jurček

subject

crystallization010405 organic chemistryChemistryLigandelectron-deficient tetrahedral Fe4L4Supramolecular chemistryGeneral ChemistryNuclear magnetic resonance spectroscopyCrystal structureGeneral Medicine010402 general chemistry01 natural sciencesCatalysis0104 chemical scienceslaw.inventionCrystalCrystallographylawX-ray crystallographyCrystallizationChirality (chemistry)ta116

description

A highly electron-deficient C3-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 M4L4 cages. This homochiral T-symmetric cage containing a relatively large cavity of 330 A(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 CH3CN led to crystals containing both (ΔΔΔΔ and ΛΛΛΛ) enantiomers, while crystallization from CH3 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.

https://doi.org/10.1002/ange.201507295