配位子保護された金正二十面体を環状超原子分子に組み立て、超原子芳香族性を付与

Gold clusters with high symmetry are promising building blocks for cluster assemblies due to their distinctive electronic structure and tunable physicochemical properties. Herein, two cyclic superatomic molecules, (Ir@Au₉)₆(AuCl₂)₆Cl₁₂ and (Ir@Au₉)₁₀(AuCl₂)₁₀Cl₂₀, were constructed via a bottom-up assembly strategy involving face-sharing of Au₃ triangles based on the structure of icosahedral W@Au₁₂ clusters. Chemical bonding analyses reveal that the 30e (Ir@Au₉)₆ and 50e (Ir@Au₉)₁₀ cores in these two clusters are analogues of C₆H₆ and C₁₀H₁₀, respectively, with both exhibiting superatomic aromaticity. Furthermore, by replacing Ir with Os, the obtained (Os@Au₉)₁₀(AuCl₂)₁₀Cl₂₀ cluster can be regarded as an electronic analogue of the C₁₀ ring, featuring dual aromaticity with five in-plane and five out-of-plane delocalized superatomic orbitals. Given the large size of the superatom, the 40e (Os@Au₉)₁₀ core exhibits alternating superatomic single and triple bonds, similar to the C₁₈ ring. This work extends the concept of aromaticity from the molecule scale to superatomic-molecule architectures and provides a practicable bottom-up assemble approach for constructing cyclic clusters with superatomic aromaticity.