Hierarchical, Template‐Controlled Self‐Assembly of Two Different Organometallic Capsules from a Tetrakisimidazolium Salt

Abstract Controlling the assembly of molecular nanocapsules through metal‐carbon bonds constitutes a major challenge in the field of supramolecular organometallic chemistry. Here, we demonstrate the construction of two nanosized dodecanuclear organometallic capsules, [{Ag(CH 3 CN) 4 (BF 4 ) 8 }⊂Ag 12 ( 1 ) 6 ](BF 4 ) 5 and [(CF 3 SO 3 ) 8 ⊂Ag 12 ( 1 ) 6 ](CF 3 SO 3 ) 4 from the calix[4]resorcinarene‐based tetrakisimidazolium salts H 4 ‐ 1 (X) 4 and Ag I ions employing the metal‐carbene directed self‐assembly and hierarchical template strategies. An [Ag(CH 3 CH) 4 (BF 4 ) 8 ] 7− anion or eight triflate anions served as templates. The dodecanuclear capsules are the largest poly‐NHC‐derived assemblies known so far. Salt H 4 ‐ 1 (SbF 6 ) 4 reacts with Ag 2 O to give the tetranuclear assembly [(SbF 6 )⊂Ag 4 ( 1 ) 2 ](SbF 6 ) 3 featuring an encapsulated SbF 6 − anion. Transmetalation of the tetra‐NHC ligands from silver to gold yielded in all cases tetranuclear assemblies of type [Au 4 ( 1 ) 2 ]X 4 .