Heterometallic AuI6AgI6 Macrocyclic Cluster Templated by a Supramolecular Melamine Dimer

Abstract The application of supramolecular templates in aligning atomically precise heterometal arrays is important for pursuing functional materials. Herein, we report that a bilayered supramolecular tri‐deprotonated melamine dimer functions as an effective template in the construction of a heterometallic gold(I)‐silver(I) macrocyclic cluster [ μ 6 ‐(C 3 N 6 H 3 ) 3− ] 2 −Au I 6 Ag I 6 . X‐ray single crystal structural analysis showed that a crown‐like Au I 6 Ag I 6 macrocycle is aligned around two parallelly stacked μ 6 ‐(C 3 N 6 H 3 ) 3− moieties hold together with π–π interactions. Theoretical calculations revealed that the [ μ 6 ‐(C 3 N 6 H 3 ) 3− ] 2 motif dominantly contributes to the near‐occupied orbitals in the electronic structure, which is closely related to its luminescence properties. This work demonstrates that the supramolecular templates containing multiple symmetric binding sites may present a facile approach in the construction of functional metal clusters.