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Alloying and dealloying of Au18Cu32 nanoclusters at precise locations via controlling the electronegativity of substituent groups on thiol ligands

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  • Key Words:EXCHANGE SYNTHESIS; PHOTOLUMINESCENCE; DOPANT

  • Abstract: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-20 shell of the [Au18Cu32(SR-O)(36)](2-) or [Au18Cu32(SR-F)(36)](3-) (SR-O = -S-PhOMe; SR-F = -(SC6H3F2)-F-3,4) 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 (i.e., [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 via 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.

  • Volume:15

  • Issue:4

  • Translation or Not:no


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