Alloying and dealloying of Au 18 Cu 32 nanoclusters at precise locations via controlling the electronegativity of substituent groups on thiol ligands.

The doping site of metals in an alloy nanocluster plays a key role in determining the cluster properties. Herein, we found that alloying engineering was achieved by replacing Cu at specific positions in the second layer Cu shell of the [Au18Cu32(SR-O)36]2- or [Au18Cu32(SR-F)36]3- (SR-O = -S-PhOMe; SR-F = -SCHF) nanocluster with Au to generate a core-shell [Au20.31Cu29.69(SR-O)36]2- protected by mercaptan ligands with electron-donating substituents, which could be stable obtained compared with the alloyed nanocluster with electron-withdrawing substituent ligands. Moreover, dealloying engineering was accomplished by an electron-withdrawing substituent ligand exchange strategy (, [Au18Cu32(SR-F)36]2-). The abovementioned reaction was analyzed using single-crystal X-ray crystallography, electrospray ionization mass spectrometry, and X-ray photoelectron spectroscopy and monitored time-dependent ultraviolet-visible absorption spectroscopy. This reversible and precise location of alloying and dealloying provides the possibility for studying the relationship between the structure and properties of nanoclusters at the atomic level.