Assembling Gold Icosahedrons to Superatomic Molecules Mimicking the Bonding Rules in Molecules

Icosahedral gold clusters with high-symmetry geometry and magic electronic shells are potential candidates for cluster-assembling, while their assembling rules are still awaiting further investigation. In this work, we use the all-metal icosahedral M@Au12as a building block to assemble a series of bi-, tri-, tetra-, and penta-superatomic molecules with diverse superatomic bonding patterns via face-fusion, aiming to systemically explore the bonding rule of superatoms. Chemical bonding analyses indicate that these bi-, tri-, tetra-, and penta-superatomic molecules [M@Au12]n+/0(M = Re, W, Ta, Ti, Hf, Ir, and Pt) can be considered electronic analogues to Cl2, O2, N2, CO, O3, CO2, NCl3, and CF4molecules with single, double, triple, and multicenter bonds, respectively. In multi-superatomic molecules, the central superatom undergoes super S–P orbital hybridizations to form super σ bonds with each peripheral superatom, mimicking the bonding rules of molecules. Due to the large size of superatoms, superatomic molecules also present some distinct bonding characters in structure and relative energy compared to their analogues. This paper systemically investigated the superatomic bonding rules, giving references to further design and synthesis of superatom-assembled materials.