Template Synthesis, Metalation, and Self‐Assembly of Protic Gold(I)/(NHC)2 Tectons Driven by Metallophilic Interactions

A new protocol for the synthesis of protic bis(N-heterocyclic carbene) complexes of AuI by a stepwise metal-controlled coupling of isocyanide and propargylamine is described. They are used as tectons for the construction of supramolecular architectures through metalation and self-assembly. Notably a unique polymeric chain of CuI with alternate AuI/bis(imidazolate) bridging scaffolds and strong unsupported CuI–CuI interactions has been generated, as well as a 28-metal-atoms cluster containing a nanopiece of Cu2O trapped by peripheral AuI/bis(imidazolate) moieties.