Halogen-Bond-Assisted Guest Inclusion in a Synthetic Cavity

The confined space inside a self‐assembled cage enhanced halogen bonding (XB) between iodoperfluorocarbons (XB donors) and NO3− anions or H2O molecules (XB acceptors), as confirmed by NMR spectroscopy in solution and by X‐ray crystallography in the solid state. The cavity also bound an XB donor–acceptor pair, C6F3I3 and C6H5NMe2, in a selective pairwise fashion. Close but comfortable: Iodoperfluorocarbons were efficiently included in a self‐assembled cage owing to halogen bonding (XB) with NO3− anions or H2O molecules (see picture: C gray, N blue, O red, F green, I purple, Pd brown). The confined cavity of the cage enhanced XB, as confirmed by NMR spectroscopy in solution and X‐ray crystallography in the solid state. Pairwise selective XB between C6F3I3 and C6H5NMe2 within the cavity was also observed.