Surface Single-Atom Tailoring of a Gold Nanoparticle

Surface single-atom tailoring of a gold nanoparticle, that is, adding, removing, or replacing one surface atom on a structure-resolved nanoparticle in a controlled manner, is very exciting yet challenging and has not been hitherto achieved. Herein we report the first realization of the introduction of a single sulfur atom onto the surface of the structure-unraveled Au60S6(SCH2Ph)36 nanoparticle. Single-crystal X-ray crystallography reveals that the as-obtained nanoparticle consists of one Au17 kernel protected by one Au20S3(SCH2Ph)18 and one unprecedented Au23S4(SCH2Ph)18 motif with the introduced sulfur atom included as a tetrahedral-coordinated μ4-S. The introduced sulfur leads to the changes of both internal structure and crystallographic arrangement. Unlike the case of 6HLH arrangement in Au60S6(SCH2Ph)36 crystals, the “ABAB” arrangement in Au60S7(SCH2Ph)36 crystals enhances the solid photoluminescence of amorphous Au60S7(SCH2Ph)36 and brings a slight redshift of the maximum emission. The extensive near-infrared emission provides Au60S7(SCH2Ph)36 potential applications in some fields such as anticounterfeiting, imaging, etc.