Bimetal Doping in Nanoclusters: Synergistic or Counteractive?

Doped
nanoparticles (especially bimetal doped nanoparticles) have
attracted extensive interest not only for fundamental scientific research
but also for application purposes. However, their indefinite composition
(structure) and broad distribution hinder an insightful understanding
of the interaction between these invasive metals in bimetal doped
nanoparticles. Fortunately, atom-precise bimetal doped ultrasmall
nanoparticles (nanoclusters) provide opportunities to obtain such
insights. However, atom-precise trimetal nanoclusters and their structures
have rarely been reported. Here, we successfully dope thiolated Au25 nanoclusters with Hg and Ag successively by using a biantigalvanic
reduction method. We then fully characterize the as-obtained trimetal
nanoclusters using multiple techniques (including single-crystal X-ray
crystallography), and we demonstrate that the mercury and silver dopings
exhibit not only a synergistic but also a counteractive influence
on some of the physicochemical properties of Au25.