Tetrameric and Dimeric [N⋅⋅⋅I ⋅⋅⋅N] Halogen-Bonded Supramolecular Cages.

Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag -complexes. Selective formation of discrete tetrameric I L and dimeric I L halonium cages, wherein multiple [N⋅⋅⋅I ⋅⋅⋅N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF ) , and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I L1 (PF ) and I L2 (PF ) , were obtained through the [N⋅⋅⋅Ag ⋅⋅⋅N]→ [N⋅⋅⋅I ⋅⋅⋅N] cation exchange reaction between the corresponding Ag L1 (PF ) and Ag L2 (PF ) coordination cages, prepared as intermediates, and I . The synthesized metallo- and halonium cages were studied in solution by NMR, in gas phase by ESI-MS and in the solid-state by single crystal X-ray diffraction.