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This study succeeded in obtaining three new thiolate protected metal nanoclusters by changing the ligand-exchange condition from previous studies.

Metal nanoclusters composed of noble elements such as gold (Au) or silver (Ag) are regarded as superatoms. In recent years, the understanding of Au-based superatomic molecules has gradually progressed. 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 Ag13−xMx 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.

Alloying has been studied actively for thiolate (SR)-protected metal nanoclusters (NCs) because heteroatom mixing enables the creation of novel electronic structures, physical/chemical properties, ...

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [Ag

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [Ag23Pd2(PPh3)10Cl7]0 (Pd = palladium, PPh3 = triphenylphosphine, Cl = chloride), in which two icosahedral 13-atom NCs are connected, and elucidated its geometric and electronic structures to clarify what type of superatomic molecules can be synthesized. The results revealed that [Ag23Pd2(PPh3)10Cl7]0 is a synthesizable superatomic molecule. Single crystal x-ray diffraction analysis showed that the metal-metal distances in and between the icosahedral structures of [Ag23Pd2(PPh3)10Cl7]0 are slightly shorter than those of previously reported [Ag23Pt2(PPh3)10Cl7]0, whereas the metal-PPh3 distances are slightly longer. On the basis of several experiments and density functional theory calculations, we concluded that [Ag23Pd2(PPh3)10Cl7]0 and previously reported [Ag23Pt2(PPh3)10Cl7]0 are more stable than [Ag25(PPh3)10Cl7]2+ because of their stronger superatomic frameworks (metal cores). These findings are expected to lead to clear design guidelines for creation of new superatomic molecules.