A Nanocluster [Ag307Cl62(SPhtBu)110]: Chloride Intercalation, Specific Electronic State, and Superstability

The controlling synthesis of novel nanoclusters of noble metals (Au, Ag) and the determination of their atomically precise structures provide opportunities for investigating their specific properties and applications. Here we report a novel silver nanocluster [Ag307Cl62((SPhBu)-Bu-t)(110)] (Ag-307) whose structure is determined by X-ray single crystal diffraction. The structure analysis shows that nanocluster Ag-307 contains a Ag-167 core, a surface shell of [Ag140Cl2S110], and a Cl(60 )intermediate layer located between Ag-167 and [Ag140Cl2S110]. It is a first example that such many chlorides are intercalated into a Ag nanocluster. Chlorides are released in situ from solvent CHCl3. Nanocluster Ag-307 exhibits superstability. Differential pulse voltammetry experiment reveals that Ag-307 has continuous charging/discharging behavior with a capacitance value of 1.39 aF, while the Ag-307 has a surface plasmonic feature. These characteristics show that Ag(30)7 is of metallic behavior. However, its electron paramagnetic resonance (EPR) spectra display a spin magnetic behavior which could be originated from the unpassivated dangling bonds of surface atoms. The direct capture of EPR signals can be attributed to the Cl- intercalating layer which partly suppresses the electronic interactions between core and surface atoms, resulting in the relatively independent electronic states for core and surface atoms.

Automated summary

This study introduces a novel silver nanocluster Ag-307, with its structure and properties detailed analyzed, demonstrating its special stability and unique electronic characteristics.