Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages
Turunen, L., Peuronen, A., Forsblom, S., Kalenius, E., Lahtinen, M., & Rissanen, K. (2017). Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages. Chemistry: A European Journal, 23 (48), 11714-11718. doi:10.1002/chem.201702655
Published inChemistry: A European Journal
© 2017 Wiley-VCH Verlag GmbH &Co. This is a final draft version of an article whose final and definitive form has been published by Wiley-VCH. Published in this repository with the kind permission of the publisher.
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.