Abstract:Tremendous research efforts have been spent on thiolated gold nanoparticles and self-assembled monolayers of thiolate (RS-) on gold, but thiolated gold nanowires have received almost no attention. Here we computationally design two such one-dimensional nanosystems by creating a linear chain of Au icosahedra, fused together by either vertex sharing or face sharing. Then neighboring Au icosahedra are bridged by five thiolate groups for the vertex-sharing model and three RS-Au-SR motifs for the face-sharing model… Show more
“…To date, several studies have been published on the assembly of ligand-protected metal clusters. For example, Jiang et al 36 performed density functional theory (DFT) calculations on one-dimensional (1D) connected structures (1D-CS) in which Au 13 clusters were linked via a single Au atom. They theoretically predicted that such 1D-CS would exhibit different properties depending on the charge state of the metal clusters (metal or semiconductor).…”
This study demonstrates that controlling intra-cluster ligand interactions is important to obtain an assembled structure with the desired connecting structures.
“…To date, several studies have been published on the assembly of ligand-protected metal clusters. For example, Jiang et al 36 performed density functional theory (DFT) calculations on one-dimensional (1D) connected structures (1D-CS) in which Au 13 clusters were linked via a single Au atom. They theoretically predicted that such 1D-CS would exhibit different properties depending on the charge state of the metal clusters (metal or semiconductor).…”
This study demonstrates that controlling intra-cluster ligand interactions is important to obtain an assembled structure with the desired connecting structures.
“…Jiang recently predicted poly‐icosahedra connected by different modes, in which each icosahedron is connected by five thiolate or three Au–SR oligomers to form vertex‐sharing or facet‐sharing type bonds. These polymers will show different electrical conduction properties depending on their superatomic bonding (Figure ) …”
“… Structure of (a) vertex‐sharing and (b) face‐sharing poly‐icosahedra. Reproduced with permission from reference . Copyright 2009 A merican Chemical Society.…”
Clusters of gold atoms can be viewed as superatoms, in which valence electrons confined in the particles occupy atomic-like, discrete electronic levels. Chemical modification of the gold superatoms and their aggregated molecules (superatomic molecules) with organic ligands is a promising approach for their application as the building units of new functional materials. This account surveys the present status of the rapidly growing field of gold superatoms and superatomic molecules protected by thiolates and phosphines. The major aim of this article is to provide a simple picture for the structure, stability and bonding scheme of chemically modified superatoms and superatomic molecules for the development of a new class of hierarchical materials.
“…From then on, researchers started to study the evolution of structure-related properties by linear assembly of icosahedral Au 13 building blocks into longer gold clusters of clusters. 43,44 Nobusada et al theoretically predicted the structure and electronic properties of a linear triicosahedral gold cluster ([Au 37 (PH 3 ) 10 (SCH 3 ) 10 Cl 2 ] þ ) in 2007. 43 However, there has been no experimental success in the synthesis of the tri-icosahedral Au 37 nanocluster due to the increasing difficulty in linearly assembling more icosahedral Au 13 units together, albeit a cyclic 37-atom tri-icosahedral AgÀAu structure was reported in much earlier work.…”
mentioning
confidence: 99%
“…This HOMOÀLUMO gap is smaller than that of [Au 25 (PPh 3 ) 10 (SC 2 H 4 Ph) 5 Cl 2 ] 2þ (1.53 eV) as well as that of [Au 13 (PPh 3 ) 8 X 2 ] 3þ (1.76 eV) but larger than those of the infinite 1D analogues of different charges (the gaps are about 0.3 and 0.2 eV for the þ2 and À2 states of the vertex-sharing wire, respectively), illustrating the general trend ; the larger the cluster, the smaller the HOMOÀLUMO gap. 44,46 Catalytic Activity of Au 37 /TiO 2 for CO Oxidation. We further investigated the catalytic activity of the Au 37 nanocluster toward CO oxidation.…”
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.
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