Homo‐ and Heteroligand Poly‐NHC Metal Assemblies: Synthesis by Narcissistic and Social Self‐Sorting

Homoleptic and heteroleptic cylinder‐shaped poly‐NHC metallosupramolecular assemblies [Ag 3 ( L ) 2 ](BF 4 ) 3 have been prepared by control of the shape, size, and electronic properties of disk‐shaped trisimidazolium salts of type H 3 ‐ L (BF 4 ) 3 . Both imidazolium salts with an electron‐deficient triazine backbone H 3 ‐ A (BF 4 ) 3 or an electron‐rich benzene backbone H 3 ‐ D (BF 4 ) 3 have been employed. Reaction of H 3 ‐ A (BF 4 ) 3 or H 3 ‐ D (BF 4 ) 3 with Ag 2 O yield trinuclear homoligand complexes [Ag 3 ( L ) 2 ](BF 4 ) 3 (L= A , D ). However, equimolar mixtures of H 3 ‐ A (BF 4 ) 3 and H 3 ‐ D (BF 4 ) 3 react with Ag 2 O under social self‐sorting to give the heteroligand assembly [Ag 3 ( A )( D )](BF 4 ) 3 . The same heteroligand assembly was obtained by transmetallation from mixtures of complexes [Ag 3 ( A ) 2 ](BF 4 ) 3 and [Ag 3 ( D ) 2 ](BF 4 ) 3 . The transmetallation from [Ag 3 ( A )( D )](BF 4 ) 3 to [Au 3 ( A )( D )](BF 4 ) 3 is also demonstrated. The study expands to concepts of narcissistic and social self‐sorting from classical Werner‐type ligands to organometallic NHC chemistry thereby opening new routes for the construction of poly‐NHC metal assemblies with increasing complexity.