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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 calix4resorcinarene‐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.
Li et al. (Thu,) studied this question.