Assembling Ligand-Protected Gold Icosahedrons into Cyclic Superatomic Molecules with Superatomic Aromaticity

Area of Science:

• * Superatomic chemistry and cluster science.
• * Exploration of novel materials with unique electronic properties.

Background:

• * High-symmetry gold clusters are key building blocks for cluster assemblies.
• * Distinctive electronic structures and tunable properties drive research in cluster science.

Purpose of the Study:

• * To construct cyclic superatomic molecules using a bottom-up assembly strategy.
• * To investigate the electronic properties and aromaticity of these novel clusters.
• * To extend the concept of aromaticity to superatomic-molecule architectures.

Main Methods:

• * Bottom-up assembly strategy involving face-sharing of gold triangles.
• * Utilized icosahedral W@Au12 clusters as structural templates.
• * Chemical bonding analyses to understand electronic structures and aromaticity.

Main Results:

• * Synthesized two cyclic superatomic molecules: (Ir@Au9)6(AuCl2)6Cl12 and (Ir@Au9)10(AuCl2)10Cl20.
• * Identified superatomic aromaticity in the (Ir@Au9)6 and (Ir@Au9)10 cores, analogous to C6H6 and C10H10.
• * Discovered dual aromaticity in an Os-containing analogue, featuring delocalized superatomic orbitals and alternating superatomic bonds.

Conclusions:

• * The concept of aromaticity is successfully extended from molecular to superatomic scales.
• * A practical bottom-up assembly method for creating cyclic clusters with superatomic aromaticity is established.
• * These findings pave the way for designing advanced cluster assemblies with tailored properties.