Tetrameric and Dimeric [N⋅⋅⋅I+⋅⋅⋅N] Halogen‐Bonded Supramolecular Cages

Abstract Tripodal N ‐donor ligands are used to form halogen‐bonded assemblies via structurally analogous Ag + ‐complexes. Selective formation of discrete tetrameric I 6 L 4 and dimeric I 3 L 2 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 6 ) 3 , and flexible ligand 1,3,5‐tris(imidazole‐1‐ylmethyl)‐2,4,6‐trimethylbenzene, L2 , respectively. The iodonium cages, I 6 L1 4 (PF 6 ) 18 and I 3 L2 2 (PF 6 ) 3 , were obtained through the [N⋅⋅⋅Ag + ⋅⋅⋅N]→ [N⋅⋅⋅I + ⋅⋅⋅N] cation exchange reaction between the corresponding Ag 6 L1 4 (PF 6 ) 18 and Ag 3 L2 2 (PF 6 ) 3 coordination cages, prepared as intermediates, and I 2 . 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.