Heterometallic Au^I ₆ Ag^I ₆ Macrocyclic Cluster Templated by a Supramolecular Melamine Dimer

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 [μ₆ -(C₃ N₆ H₃ )^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 μ₆ -(C₃ N₆ H₃ )^3- moieties hold together with π-π interactions. Theoretical calculations revealed that the [μ₆ -(C₃ N₆ H₃ )^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.