Controlled Sequential Doping of Metal Nanocluster

Abstract

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 Au 25 Cd 1 (p-MBT) 17 (PPh 3 ) 2 , Au 18 Cd 2 (p-MBT) 14 (PPh 3 ) 2 , and [Au 19 Cd 3 (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.

89Zr-Labeled pH-Responsive Gold Nanoclusters for Radiosensitization Therapy of Tumors

“…The predominant peak observed at 5308 Da corresponded to [Au 25 S 12 ] − , which has been identified as the primary mass fragment in the mass spectral fragmentation of Au 25 (SR) 18 nanoclusters (where R = GSH or l -Cys). ,, Additional fragments detected included [Au 21 S 10 ] − , [Au 22 S 11 ] − , [Au 23 S 11 ] − , [Au 23 S 11 ] − , [Au 27 S 13 ] − , and [Au 29 S 14 ] − , indicative of the consistent loss of Au and S atoms. Therefore, in accordance with our previous simulations, high radiolabeling stability may arise from the fact that 68 Ga could substitute the central Au atom, while 89 Zr replaces the Au atom in the shell of the Au 13 icosahedron in Au 25 (SR) 18 nanoclusters. − Importantly, the 89 Zr and 68 Ga labeling did not affect the size, charge, or pH-responsive aggregation property of the nanoclusters (Supporting Information, Figures S14–S19).…”

Multiple synthesis routes for atomically precise noble metal nanoclusters

“…For metal nanoclusters, the fine control of inherent features, including the size, shape, composition, state of aggregation, atomic packing model and crystallographic arrangement, can effectively tailor their properties. 42–53 Normally, replacing the central metal atom in the inner structure ( e.g. , core) of a cluster with a heteroatom ( e.g.…”