5 years ago

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

Tetrameric and Dimeric [N⋅⋅⋅I+⋅⋅⋅N] Halogen-Bonded Supramolecular Cages
Kari Rissanen, Manu Lahtinen, Lotta Turunen, Anssi Peuronen, Samu Forsblom, Elina Kalenius
Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag+-complexes. Selective formation of discrete tetrameric I6L4 and dimeric I3L2 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(PF6)3, and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I6L14(PF6)18 and I3L22(PF6)3, were obtained through the [N⋅⋅⋅Ag+⋅⋅⋅N] [N⋅⋅⋅I+⋅⋅⋅N] cation exchange reaction between the corresponding Ag6L14(PF6)18 and Ag3L22(PF6)3 coordination cages, prepared as intermediates, and I2. 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. My body is a cage: Applying the robust [N⋅⋅⋅Ag+⋅⋅⋅N][N⋅⋅⋅I+⋅⋅⋅N] cation exchange reaction to silver metallocages from tripodal N-donor halogen ligands results in the corresponding halonium cages (see figure).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702655

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