Direct assembly between closed-shell coinage metal superatoms

Bottom-up constructing all-metal functional materials is challenging, because the metal clusters are prone to lose their original structures during coalensence. In this work, we report that closed-shell coinage metal superatoms can achieve direct chemical bonding without losing their electronic properties. The reason is that the supermolecule formed by two superatoms has the same number of bonding and anti-bonding supermolecular orbitals, in which the bonding orbitals contribute to bonding and the anti-bonding orbitals with anti-phase orbitals delocalized over each monomer to maintain the individual geometric and electronic structural properties. Further analysis indicates the interactions between two superatoms are too weak to break the structure of monomers, which is confirmed by the first-principles molecular dynamics simulations. With these superatoms as the basic units, a series of robust one-dimensional and two-dimensional nanostructures are fabricated. Our findings provide a general strategy to take advantage of superatoms in regulating bonding compared to natural atoms, which paves the way for the bottom-up design of materials with collective properties.