Ligand symmetry-equivalence on thiolate protected gold nanoclusters determined by NMR spectroscopy

O. Andrea Wong; Christine L. Heinecke; Ashli R. Simone; Robert L. Whetten; Christopher J. Ackerson

doi:10.1039/c2nr30259d

Ligand symmetry-equivalence on thiolate protected gold nanoclusters determined by NMR spectroscopy

O. Andrea Wong, Christine L. Heinecke, Ashli R. Simone, Robert L. Whetten, Christopher J. Ackerson

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71 Scopus citations

Abstract

The Au₁₄₄(SR)₆₀ nanocluster has been a subject of structural conjecture since its initial description over a decade ago as a 29 kDa compound, yet a decisive empirical structure is elusive. Herein we show that ¹H NMR spectroscopy can provide a detailed view of ligand-layer equivalence for thiolate protected gold nanoclusters. We show that Au ₂₅(SR)₁₈, Au₃₈(SR)₂₄ and Au ₁₀₂(SR)₄₄ nanoclusters have ¹H NMR spectra where the number of distinct chemical environments for the R-groups is equivalent to the number of symmetry environments of the sulfur headgroups, which anchor each ligand. We also show that the Au₁₄₄(SR) ₆₀¹H NMR spectrum is consistent with a previously published DFT-derived structural model for Au₁₄₄(SR)₆₀. We suggest that this analysis may be extended to other structurally obscure nanoclusters, such as a ∼59 kDa compound for which we observe up to four symmetry environments.

Original language	English (US)
Pages (from-to)	4099-4102
Number of pages	4
Journal	Nanoscale
Volume	4
Issue number	14
DOIs	https://doi.org/10.1039/c2nr30259d
State	Published - Jul 21 2012
Externally published	Yes

ASJC Scopus subject areas

General Materials Science

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title = "Ligand symmetry-equivalence on thiolate protected gold nanoclusters determined by NMR spectroscopy",

abstract = "The Au144(SR)60 nanocluster has been a subject of structural conjecture since its initial description over a decade ago as a 29 kDa compound, yet a decisive empirical structure is elusive. Herein we show that 1H NMR spectroscopy can provide a detailed view of ligand-layer equivalence for thiolate protected gold nanoclusters. We show that Au 25(SR)18, Au38(SR)24 and Au 102(SR)44 nanoclusters have 1H NMR spectra where the number of distinct chemical environments for the R-groups is equivalent to the number of symmetry environments of the sulfur headgroups, which anchor each ligand. We also show that the Au144(SR) 601H NMR spectrum is consistent with a previously published DFT-derived structural model for Au144(SR)60. We suggest that this analysis may be extended to other structurally obscure nanoclusters, such as a ∼59 kDa compound for which we observe up to four symmetry environments.",

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AU - Wong, O. Andrea

AU - Heinecke, Christine L.

AU - Simone, Ashli R.

AU - Whetten, Robert L.

AU - Ackerson, Christopher J.

PY - 2012/7/21

Y1 - 2012/7/21

N2 - The Au144(SR)60 nanocluster has been a subject of structural conjecture since its initial description over a decade ago as a 29 kDa compound, yet a decisive empirical structure is elusive. Herein we show that 1H NMR spectroscopy can provide a detailed view of ligand-layer equivalence for thiolate protected gold nanoclusters. We show that Au 25(SR)18, Au38(SR)24 and Au 102(SR)44 nanoclusters have 1H NMR spectra where the number of distinct chemical environments for the R-groups is equivalent to the number of symmetry environments of the sulfur headgroups, which anchor each ligand. We also show that the Au144(SR) 601H NMR spectrum is consistent with a previously published DFT-derived structural model for Au144(SR)60. We suggest that this analysis may be extended to other structurally obscure nanoclusters, such as a ∼59 kDa compound for which we observe up to four symmetry environments.

AB - The Au144(SR)60 nanocluster has been a subject of structural conjecture since its initial description over a decade ago as a 29 kDa compound, yet a decisive empirical structure is elusive. Herein we show that 1H NMR spectroscopy can provide a detailed view of ligand-layer equivalence for thiolate protected gold nanoclusters. We show that Au 25(SR)18, Au38(SR)24 and Au 102(SR)44 nanoclusters have 1H NMR spectra where the number of distinct chemical environments for the R-groups is equivalent to the number of symmetry environments of the sulfur headgroups, which anchor each ligand. We also show that the Au144(SR) 601H NMR spectrum is consistent with a previously published DFT-derived structural model for Au144(SR)60. We suggest that this analysis may be extended to other structurally obscure nanoclusters, such as a ∼59 kDa compound for which we observe up to four symmetry environments.

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Ligand symmetry-equivalence on thiolate protected gold nanoclusters determined by NMR spectroscopy

Abstract

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