Encapsulation of Halocarbons in a Tetrahedral Anion Cage

Caged supramolecular systems are promising hosts for guest inclusion, separation, and stabilization. Well-studied examples are mainly metal-coordination-based or covalent architectures. An anion-coordination-based cage that is capable of encapsulating halocarbon guests is reported for the first time. This A(4)L(4)-type (A=anion) tetrahedral cage, [(PO4)(4)L-4](12-), assembled from a C-3-symmetric tris(bisurea) ligand (L) and phosphate ion (PO43-), readily accommodates a series of quasi-tetrahedral halocarbons, such as the Freon components CFCl3, CF2Cl2, CHFCl2, and C(CH3)F-3, and chlorocarbons CH2Cl2, CHCl3, CCl4, C(CH3)Cl-3, C(CH3)(2)Cl-2, and C(CH3)(3)Cl. The guest encapsulation in the solid state is confirmed by crystal structures, while the host-guest interactions in solution were demonstrated by NMR techniques.