A Nanocluster [Ag₃₀₇Cl₆₂(SPh^<i>t</i>Bu)₁₁₀]: Chloride Intercalation, Specific Electronic State, and Superstability

Abstract

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(SPh^<i>t</i>Bu)₁₁₀] (Ag₃₀₇) whose structure is determined by X-ray single crystal diffraction. The structure analysis shows that nanocluster Ag₃₀₇ contains a Ag₁₆₇ core, a surface shell of [Ag₁₄₀Cl₂S₁₁₀], and a Cl₆₀ intermediate layer located between Ag₁₆₇ 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 Ag₃₀₇ exhibits superstability. Differential pulse voltammetry experiment reveals that Ag₃₀₇ has continuous charging/discharging behavior with a capacitance value of 1.39 aF, while the Ag₃₀₇ has a surface plasmonic feature. These characteristics show that Ag₃₀₇ 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.