Atomically Precise Ternary Cluster: Polyoxometalate Cluster Sandwiched by Gold Clusters Protected by N‐Heterocyclic Carbenes

Coinage metal (Au, Ag, Cu) cluster and polyoxometalate (POM) cluster represent two types of subnanometer "artificial atoms" with significant potential in catalysis, sensing, and nanomedicine. While composite clusters combining Ag/Cu clusters with POM have achieved considerable success, the assembly of gold clusters with POM is still lagging. Herein, we first designedly synthesized two cluster structural units: an Au₃O cluster stabilized by diverse N-heterocyclic carbene (NHC) ligands and an amine-terminated POM linker. The subsequent reaction involved amine substitution in the POM linker for the central O atom in the Au₃O cluster, resulting in the first ternary composite cluster-a POM cluster sandwiched by two Au clusters protected by NHCs. Single-crystal X-ray diffraction and other characteristic methods characterized their atomically precise structures. Furthermore, altering the NHC ligands decreased the number of gold atoms in the sandwich structures, accompanying the different protonated degrees of amine ligand in the terminal end of the POM linker. These composite clusters showed excellent performances in catalytic H₂O₂ conversion through the synergistic effect between gold clusters and POM clusters. This work opens a new avenue to functional composite metal clusters and would promote their enhanced catalysis applications through intercluster synergistic interactions within composite systems.