Controlled Sequential Doping of Metal Nanocluster

Atomically precise doping of metal nanoclusters provides
excellent
opportunities not only for subtly tailoring their properties but also
for in-depth understanding of composition (structure)–property
correlation of metal nanoclusters and has attracted increasing interest
partly due to its significance for fundamental research and practical
applications. Although single and multiple metal atom doping of metal
nanoclusters (NCs) has been achieved, sequential single-to-multiple
metal atom doping is still a big challenge and has not yet been reported.
Herein, by introducing a second ligand, a novel multistep synthesis
method was developed, controlled sequential single-to-multiple metal
atom doping was successfully achieved for the first time, and three
doped NCs Au25Cd1(p-MBT)17(PPh3)2, Au18Cd2(p-MBT)14(PPh3)2, and [Au19Cd3(p-MBT)18]− (p-MBTH: para-methylbenzenethiol) were obtained, including two novel NCs that
were precisely characterized via mass spectrometry, single-crystal
X-ray crystallography, and so forth. Furthermore, sequential doping-induced
evolutions in the atomic and crystallographic structures and optical
and catalytic properties of NCs were revealed.