28 kDa Alkanethiolate-Protected Au Clusters Give Analogous Solution Electrochemistry and STM Coulomb Staircases

Ingram, Roychelle S.; Hostetler, Michael J.; Murray, Royce W.; Schaaff, T. Gregory; Khoury, Joseph T.; Whetten, Robert L.; Bigioni, Terry P.; Guthrie, D. K.; First, Phillip N.

doi:10.1021/ja972319y

Cited by 303 publications

(332 citation statements)

References 14 publications

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“…11c) based on the optimized cluster is in good agreement with the experimental one, and the computed optical gap (1.3 eV) is also close to the experimental value (1.5 eV). In light of the predicted core structure of Au 19 (SR) 13 , the vertex-truncated icosahedral Au 11 -core is closely related to that in Au 25 (SR) 18 . The Au 19 (SR) 13 cluster is considered as an important intermediate towards the formation of Au 25 (SR) 18 from smaller clusters.…”

Section: 'Staple Fitness' and Force-field Based ''Divide-and-protect'mentioning

confidence: 94%

“…Nobusada et al constructed two types of Au 25 -core, one with a face-centered-cubic (FCC) structure with six Au(111) facets consisting of eight gold atoms (FCC-Au 25 -core), and another with a vertex-shared biicosahedral structure (SES-Au 25 -core). The selection of SESAu 25 -core is partially motivated by the finding of a vertex-shared bi-icosahedral Au 25 -core in [Au 25 (PPh 3 ) 10 (SR) 5 Cl 2 ] 2+ . 91 With both types of Au 25 -core, the 18 thiol ligands were manually placed on the Au 25 -core followed by a DFT optimization based on the Lee-Yang-Parr correlation functional (B3LYP).…”

Section: Information Required For Predicting the Structure Of A Complmentioning

confidence: 99%

“…It is worthy of quoting one sentence in a perspective article by Whetten et al on the structure of Au 102 (p-MBA) 44 : 65 ''The known properties of nanoscale clusters can now be rationalized in terms of atomic ordering.'' The term ''atomic ordering'' was also applicable in describing another successfully crystallized thiolate-protected gold cluster, Au 25 5 ] e where a, a 0 , b, c, d and e are integers that satisfy certain constraints. 63 This view is also consistent with the ''divide-and-protect'' concept.…”

Section: Introductionmentioning

confidence: 99%

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Investigating the structural evolution of thiolate protected gold clusters from first-principles

2012

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Unlike bulk materials, the physicochemical properties of nano-sized metal clusters can be strongly dependent on their atomic structure and size. Over the past two decades, major progress has been made in both the synthesis and characterization of a special class of ligated metal nanoclusters, namely, the thiolate-protected gold clusters with size less than 2 nm. Nevertheless, the determination of the precise atomic structure of thiolate-protected gold clusters is still a grand challenge to both experimentalists and theorists. The lack of atomic structures for many thiolate-protected gold clusters has hampered our in-depth understanding of their physicochemical properties and size-dependent structural evolution. Recent breakthroughs in the determination of the atomic structure of two clusters, [Au 25 (SCH 2 CH 2 Ph) 18 ] q (q ¼ À1, 0) and Au 102 (p-MBA) 44 , from X-ray crystallography have uncovered many new characteristics regarding the gold-sulfur bonding as well as the atomic packing structure in gold thiolate nanoclusters. Knowledge obtained from the atomic structures of both thiolate-protected gold clusters allows researchers to examine a more general ''inherent structure rule'' underlying this special class of ligated gold nanoclusters. That is, a highly stable thiolate-protected gold cluster can be viewed as a combination of a highly symmetric Au core and several protecting gold-thiolate ''staple motifs'', as illustrated by a general structural formula [Au]

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Section: 'Staple Fitness' and Force-field Based ''Divide-and-protect'mentioning

confidence: 94%

Section: Information Required For Predicting the Structure Of A Complmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Investigating the structural evolution of thiolate protected gold clusters from first-principles

2012

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“…[3][4][5][6] At ambient temperature, both freely diffusing and electrode-attached MPCs demonstrate the voltammetric responses featuring a series of evenly spaced current peaks. 4,[7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] This ensemble behavior is equivalent to a series of classical Coulomb staircase charging events or sequential electrochemical redox reactions, which occur as MPCs encompass an intermediate dimension between small molecules and bulk materials.…”

Section: Introductionmentioning

confidence: 99%

Absolute Standard Redox Potential of Monolayer-Protected Gold Nanoclusters

2005

J. Phys. Chem. B

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The redox properties of monolayer-protected gold nanoclusters (MPCs) are considered from both the theoretical and experimental viewpoints. The "absolute standard redox potential" ([E Z/Z-1 0 ] abs ) of MPCs is first derived from electrostatic considerations. A linear dependence of the absolute standard redox potential on the valence state of MPCs is theoretically predicted and verified experimentally. By employing ferricinium/ferrocene (Fc + /Fc) as a reference redox couple, the average valence state of MPCs at a given potential can be estimated.

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“…Thus there have been structural and spectroscopic studies. Electrical transport properties (8), phase transitions of the alkyl chains (9), reactivity of the terminal groups (10), and exchange behavior (11) of the adsorbates have all been studied. Most of these investigations have been centered around the Au-alkanethiol system, mostly because of the wealth of knowledge of the corresponding 2D SAMs (12, 13).…”

Section: Introductionmentioning

confidence: 99%

3D Monolayers of 1,4-Benzenedimethanethiol on Au and Ag Clusters: Distinct Difference in Adsorption Geometry with the Corresponding 2D Monolayers

Venkataramanan

Pradeep

1999

Journal of Colloid and Interface Science

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Au and Ag clusters of 3-nm mean diameter were prepared with 1,4-benzenedimethanethiol (BDMT) as the capping molecule. In both the monolayer-capped clusters, BDMT adsorbs in the dithiolate form in contrast to in the 2D monolayers, where the dithiolate form exists only in the case of Ag. As a result, the molecule lies flat on the cluster surface in both Au and Ag, whereas the molecular plane is perpendicular to the surface in the 2D monolayer of Au. This difference in adsorbate structure is attributed to the evolution in the cluster surface as adsorption occurs. Transmission electron microscopy and X-ray powder diffraction suggest that no superlattice of the clusters exists. Mass spectrometry suggests the presence of the phase transfer reagent at the surface. X-ray photoelectron spectroscopy confirms the chemical similarity of the two surfaces and suggests that the thiolate at the surface is susceptible to X-ray beam induced damage.

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28 kDa Alkanethiolate-Protected Au Clusters Give Analogous Solution Electrochemistry and STM Coulomb Staircases

Cited by 303 publications

References 14 publications

Investigating the structural evolution of thiolate protected gold clusters from first-principles

Investigating the structural evolution of thiolate protected gold clusters from first-principles

Absolute Standard Redox Potential of Monolayer-Protected Gold Nanoclusters

3D Monolayers of 1,4-Benzenedimethanethiol on Au and Ag Clusters: Distinct Difference in Adsorption Geometry with the Corresponding 2D Monolayers

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