Synthesis and Characterization of Poly?NHC?Derived Silver(I) Assemblies and Their Transformation into Poly?Imidazolium Macrocycles

Three metallosupramolecular assemblies composed of two bis-NHCs and silver atoms, [4](PF6)2, tetra-NHCs four [7](PF6)4, tri-NHCs three atoms [8](BF4)3, have been prepared. Assemblies [4](PF6)2 [7](PF6)4 feature NHC ligands decorated with terminal olefin groups. Irradiation yielded complex [5](PF6)2 cyclobutane rings linking the bis-NHC ligands. Liberation macrocyclic tetrakisimidazolium salt H4-6(PF6)4 was achieved by reaction NH4Cl/NH4PF6. No [2+2] cycloaddition observed upon irradiation apparently due to an unfavorable orientation [8](BF4)3 internal pairs groups leads [9](BF4)3 as a mixture isomers that differ on relative rings. Reaction NH4Cl/NH4BF4 yields isomer novel cage-line hexakisimidazolium H6-10(BF4)6.