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Tetrameric and Dimeric [N⋅⋅⋅I + ⋅⋅⋅N] Halogen‐Bonded Supramolecular Cages
Author(s) -
Turunen Lotta,
Peuronen Anssi,
Forsblom Samu,
Kalenius Elina,
Lahtinen Manu,
Rissanen Kari
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702655
Subject(s) - chemistry , mesitylene , steric effects , halogen , ligand (biochemistry) , crystallography , supramolecular chemistry , cationic polymerization , imidazole , stereochemistry , solid state , crystal structure , polymer chemistry , toluene , organic chemistry , alkyl , receptor , biochemistry
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.