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 Au60 S6 (SCH2 Ph)36 nanoparticle. Single-crystal X-ray crystallography reveals that the as-obtained nanoparticle consists of one Au17 kernel protected by one Au20 S3 (SCH2 Ph)18 and one unprecedented Au23 S4 (SCH2 Ph)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 Au60 S6 (SCH2 Ph)36 crystals, the "ABAB" arrangement in Au60 S7 (SCH2 Ph)36 crystals enhances the solid photoluminescence of amorphous Au60 S7 (SCH2 Ph)36 and brings a slight redshift of the maximum emission. The extensive near-infrared emission provides Au60 S7 (SCH2 Ph)36 potential applications in some fields such as anticounterfeiting, imaging, etc.