Tri-icosahedral Gold Nanocluster [Au37(PPh3)10(SC2H4Ph)10X2]+: Linear Assembly of Icosahedral Building Blocks

• Published in: ACS nano Vol. 9; no. 8; pp. 8530 - 8536
• Main Authors: Jin, Renxi, Liu, Chong, Zhao, Shuo, Das, Anindita, Xing, Hongzhu, Gayathri, Chakicherla, Xing, Yan, Rosi, Nathaniel L, Gil, Roberto R, Jin, Rongchao
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25.08.2015
• Subjects: clusters of clusters; CO oxidation; mixed ligands; structure evolution; Au37 nanocluster
• ISSN: 1936-0851; 1936-086X
• DOI: 10.1021/acsnano.5b03524

The [Au37(PPh3)10(SR)10X2]+ 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 [Au37(PPh3)10(SC2H4Ph)10X2]+ (counterion: Cl– or Br–) with its crystal structure characterized by X-ray crystallography. This nanocluster shows a rod-like structure assembled from three icosahedral Au13 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 clusters). Some interesting trends are identified in the evolution from the monoicosahedral [Au13(PPh3)10X2]3+ to the bi-icosahedral [Au25(PPh3)10(SC2H4Ph)5X2]2+ and to the tri-icosahedral [Au37(PPh3)10(SC2H4Ph)10X2]+ nanocluster, which also points to the possibility of achieving even longer rod nanoclusters based upon assembly of icosahedral building blocks.