Tailoring optical and photocatalytic properties by single-Ag-atom exchange in Au13Ag12(PPh3)10Cl8 nanoclusters

Precise mono-doping of metal atom into metal particles at a specific particle position (e.g., the central site) in a highly controllable manner is still a challenge. In this work, we develop a highly controllable strategy for exchanging a single Ag atom into the central gold site of Au13Ag12(PPh3)(10)Cl-8 (Ph = phenyl) nanoclusters. Interestingly, a pigeon-pair cluster of {[Au13Ag12(PPh3)(10)Cl-8]center dot[Au12Ag13(PPh3)(10)Cl-8]}(2)(+) is obtained and confirmed by electrospray ionization mass spectrometry (ESI-MS), thermogravimetric analysis (TGA) and single crystal X-ray diffraction (SCXRD) analysis. The experimental results and density functional theory (DFT) calculations suggest that the single-metal-atom exchanging from [Au13Ag12(PPh3)(10)Cl-8](+) to [Au12Ag13(PPh3)(10)Cl-8](+) occurs at the central position through the side entry of the mu(3)-bridging CI atoms. Finally, the effects on the electronic structure and properties caused by the single-atom exchange at the central site are shown by the enhancement of fluorescence and catalytic activity in the photocatalytic oxidation of ethanol.

Automated summary

A highly controllable strategy for precise mono-doping of metal atoms into metal nanoclusters was developed, resulting in a pigeon-pair cluster. Experimental results and DFT calculations demonstrated the effects of single-atom exchange on electronic structure and properties, leading to enhanced catalytic activity.