Journal
ACS NANO
Volume 9, Issue 8, Pages 8530-8536Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.5b03524
Keywords
Au-37 nanocluster; mixed ligands; clusters of clusters; structure evolution; CO oxidation
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Funding
- China Scholarship Council
- Air Force Office of Scientific Research under AFOSR [FA9550-15-1-9999 (FA9550-15-1-0154)]
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The [Au-37(PPh3)(10)(SR)(10)X-2](+) nanocluster (where SR = thiolate and X = Cl/Br) was theoretically predicted in 2007, but since then, there has been no experimental success in the synthesis and structure determination. Herein, we report a kinetically controlled, selective synthesis of [Au-37(PPh3)(10)(SC2H4Ph)(10)X-2](+) (counterion: Cl- or Br-) with its crystal structure characterized by X-ray crystallography. This nanocluster shows a rod-like structure assembled from three icosahedral Au-13 units in a linear fashion, consistent with the earlier prediction. The optical absorption and the electrochemical and catalytic properties are investigated. The successful synthesis of this new nanocluster allows us to gain insight into the size, structure, and property evolution of gold nanoclusters that are based upon the assembly of icosahedral units (i.e., cluster of dusters). Some interesting trends are identified in the evolution from the monoicosahedral [Au-13(PPh3)(10)X-2](3+) to the bi-icosahedral [Au-25(PPh3)(10)(SC2H4Ph)(5)X-2](2+) and to the tri-icosahedral [Au-37(PPh3)(10)(SC2H4Ph)(10)X-2](+) nanocluster, which also points to the possibility of achieving even longer rod nanoclusters based upon assembly of icosahedral building blocks.
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