Superatom-in-Superatom [RhH@Ag₂₄ (SPhMe₂ )₁₈ ]^2- Nanocluster

Area of Science:

• Nanomaterials Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Heterometal doping is key for tuning metal nanocluster properties.
• Doping with open d-shell metals is underexplored.
• Previous research focused on closed d-shell heterometals.

Purpose of the Study:

• To synthesize and characterize a novel nanocluster doped with an open d-shell metal.
• To explore the formation of superatomic structures within nanoclusters.
• To investigate the electronic configuration and stability of the new nanocluster.

Main Methods:

• Synthesis of [RhHAg24(SPhMe2)18]2- nanocluster.
• Experimental characterization (e.g., spectroscopy, crystallography).
• Theoretical calculations (e.g., DFT) to understand electronic structure and bonding.

Main Results:

• Successful synthesis of [RhHAg24(SPhMe2)18]2- nanocluster.
• Rh atom with open d-shells forms a RhH superatom with closed d-shells.
• The RhH dopant is isoelectronic to a Pd atom, forming a superatomic construct.
• Demonstrated the first 'superatom-in-superatom' nanocluster.

Conclusions:

• Open d-shell metal doping is feasible and leads to novel superatomic structures.
• The RhHAg24 nanocluster represents a new class of 'superatom-in-superatom' materials.
• This work expands the scope of heterometal doping in nanocluster chemistry.