Template Synthesis of Three-Dimensional Hexakisimidazolium Cages

A procedure for the synthesis of three-dimensional hexakisimidazolium cage compounds has been developed. The reaction of the trigonal trisimidazolium salts H3L(PF6)(3), decorated with three N-olefinic pendants, and silver oxide yielded trinuclear trisilver(I) hexacarbene molecular cylinders of the type [Ag3L2](3+) with the olefinic pendants from the two different tricarbene ligands arranged in three pairs. Subsequent UV irradiation gave three cyclobutane links between the two tris-NHC ligands in three [2+2] cycloaddition reactions, thereby generating a three-dimensional hexakis-NHC ligand. Removal of the metal ions resulted in the formation of three-dimensional hexakisimidazolium cages with a large internal cavity.