Metallosupramolecular poly‐NHC‐metal assemblies were prepared from trigonal hexakis (H6‐1 a(PF6)6 and H6‐1 b(PF6)6) or nonakis (H9‐3(BF4)9) imidazolium salts and Ag2O. Complexes [Ag6(1 a)2](PF6)6 and [Ag6(1 b)2](PF6)6 are built from six Ag+ ions sandwiched between two trigonal hexacarbene ligands with an inner and an outer NHC donor in each of the three ligand arms. The metal atoms are arranged in two triangles. The hexakis‐NHC ligands bear cinnamic ester groups at the outlying NHC donors, used in postsynthetic [2+2] cycloaddition reactions linking two hexakis‐NHC ligands by three cyclobutane units to give complexes [Ag6(2 a)](PF6)6 and [Ag6(2 b)](PF6)6 bearing a dodecacarbene ligand. From the related nonakisimidazolium salt H9‐3(BF4)9, complex [Ag9(4)](BF4)9 bearing an octadecacarbene ligand was obtained. Removal of the template metals yielded very large, stable, polyimidazolium cations with 12 or 18 internal imidazolium groups.
Metallosupramolecular poly-NHC-metal assemblies were prepared from trigonal hexakis (H 6 -1a(PF 6 ) 6 and H 6 -1b(PF 6 ) 6 )o rn onakis (H 9 -3(BF 4 ) 9 )i midazolium salts and Ag 2 O. Complexes [Ag 6 (1a) 2 ](PF 6 ) 6 and [Ag 6 (1b) 2 ](PF 6 ) 6 are built from six Ag + ions sandwiched between two trigonal hexacarbene ligands with an inner and an outer NHC donor in each of the three ligand arms.The metal atoms are arranged in two triangles.T he hexakis-NHC ligands bear cinnamic ester groups at the outlying NHC donors,u sed in postsynthetic [2+ +2] cycloaddition reactions linking two hexakis-NHC ligands by three cyclobutane units to give complexes [Ag 6 -(2a)](PF 6 ) 6 and [Ag 6 (2b)](PF 6 ) 6 bearing ad odecacarbene ligand. Fromthe related nonakisimidazolium salt H 9 -3(BF 4 ) 9 , complex [Ag 9 (4)](BF 4 ) 9 bearing an octadecacarbene ligand was obtained. Removal of the template metals yielded very large,s table,p olyimidazolium cations with 12 or 18 internal imidazolium groups.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 3. Synthesis of the third-generationn onanuclearassembly [Ag 9 (3) 2 ](BF 4 ) 9 followed by the preparation of the octadecakisimidazolium salt H 18 -4(PF 6 ) 18 .
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