Key factors for connecting silver-based icosahedral superatoms by vertex sharing

Metal nanoclusters composed of noble elements such as gold (Au) or silver (Ag) are regarded as superatoms. In recent years, the understanding of the materials composed of superatoms, which are often called superatomic molecules, has gradually progressed for Au-based materials. However, there is still little information on Ag-based superatomic molecules. In the present study, we synthesise two di-superatomic molecules with Ag as the main constituent element and reveal the three essential conditions for the formation and isolation of a superatomic molecule comprising two Ag 13− x M x structures (M = Ag or other metal; x = number of M) connected by vertex sharing. The effects of the central atom and the type of bridging halogen on the electronic structure of the resulting superatomic molecule are also clarified in detail. These findings are expected to provide clear design guidelines for the creation of superatomic molecules with various properties and functions. Icosahedron-based M 13 nanoclusters are common building blocks to produce atomically precise superatomic molecules, but our understanding of the chemistry governing the connection between icosahedral M 13 units is limited. Here, the key factors influencing the vertex sharing connection between Ag 13−x M x structures are studied, and the effects of different central metal atoms and the type of bridging halogen atom are clarified.