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

Homoleptic and heteroleptic cylinder-shaped poly-NHC metallosupramolecular assemblies [Ag₃ (L)₂ ](BF₄ )₃ have been prepared by control of the shape, size, and electronic properties of disk-shaped trisimidazolium salts of type H₃ -L(BF₄ )₃ . Both imidazolium salts with an electron-deficient triazine backbone H₃ -A(BF₄ )₃ or an electron-rich benzene backbone H₃ -D(BF₄ )₃ have been employed. Reaction of H₃ -A(BF₄ )₃ or H₃ -D(BF₄ )₃ with Ag₂ O yield trinuclear homoligand complexes [Ag₃ (L)₂ ](BF₄ )₃ (L=A, D). However, equimolar mixtures of H₃ -A(BF₄ )₃ and H₃ -D(BF₄ )₃ react with Ag₂ O under social self-sorting to give the heteroligand assembly [Ag₃ (A)(D)](BF₄ )₃ . The same heteroligand assembly was obtained by transmetallation from mixtures of complexes [Ag₃ (A)₂ ](BF₄ )₃ and [Ag₃ (D)₂ ](BF₄ )₃ . The transmetallation from [Ag₃ (A)(D)](BF₄ )₃ to [Au₃ (A)(D)](BF₄ )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.