A 200‐fold Quantum Yield Boost in the Photoluminescence of Silver‐Doped AgxAu25−x Nanoclusters: The 13 th Silver Atom Matters

The rod-shaped Au25 nanocluster possesses a low photoluminescence quantum yield (QY=0.1%) and hence is not of practical use in bioimaging and related applications. Herein, we show that substituting silver atoms for gold in the 25-atom matrix can drastically enhance the photoluminescence. The obtained Ag(x)Au(25-x) (x=1-13) nanoclusters exhibit high quantum yield (QY=40.1%), which is in striking contrast with the normally weakly luminescent Ag(x)Au(25-x) species (x=1-12, QY=0.21%). X-ray crystallography further determines the substitution sites of Ag atoms in the Ag(x)Au(25-x) cluster through partial occupancy analysis, which provides further insight into the mechanism of photoluminescence enhancement.