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

Abstract

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.

A grand unified model for liganded gold clusters

“…A grand challenge to scientists in this field, however, is the precise determination of atomic structures of liganded gold clusters. To date, atomic structures of tens of liganded gold clusters have been determined via X-ray crystallography56789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263. Nevertheless, these revelations appear serendipitous as the structural determination largely hinges on availability of single crystals for the liganded gold clusters.…”

Total Structure Determination of the Pt1Ag9[P(Ph‐F)3]7Cl3 Nanocluster

“…The electronic properties of the icosahedral structured M 13 nanoclusters and its assembled nanoclusters have been widely studied, and the properties of the cluster‐assembled materials could be regulated by controlling the number of the M 13 units , , , . For example, when moving from icosahedral trimers Au 37 to dimer Au 25 and to monomers Au 13 , the optical energy gap increased from 0.83 eV to 1.73 eV and to 1.96 eV . Similarly, when moving from Pt 3 Ag 33 to Pt 2 Ag 23 and to Pt 1 Ag 12 nanoclusters, the optical energy gap increased monotonically, and this was confirmed by DFT calculations, which reproduced the blue‐shift of the emission spectra .…”

Ligand-protected gold clusters: the structure, synthesis and applications

“…54 Monodispersity of a cluster is a necessary condition for its crystallization and subsequent investigation of proper- 10 Cl 2 ] + . 129 The`host ± guest' approach, as applied to the synthesis of gold clusters, is practically implemented using a-, b-and g-cyclodextrins (CD). 130,131 The cavity of the cyclodextrin molecule has the shape of a truncated cone and only small clusters can accommodate within.…”