First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands

Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally ra...

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Published inNature communications Vol. 3; no. 1; p. 798
Main Authors Dolamic, Igor, Knoppe, Stefan, Dass, Amala, Bürgi, Thomas
Format Journal Article
LanguageEnglish
Published London Nature Publishing Group UK 24.04.2012
Nature Publishing Group
Nature Pub. Group
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Abstract Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au 38 (SCH 2 CH 2 Ph) 24 , achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10 −3 . Comparison with reported circular dichroism spectra of other Au 38 clusters reveals that the influence of the ligand on the chiroptical properties is minor. Clusters of gold atoms protected with achiral thiolates can display chirality, and such chiral nanoparticles could open new possibilities in catalysis and sensing. Here, the first separation of the enantiomers of a gold cluster, protected by achiral thiolates, Au 38 (SCH 2 CH 2 Ph) 24 , is achieved.
AbstractList Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au(38)(SCH(2)CH(2)Ph)(24), achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10(-3). Comparison with reported circular dichroism spectra of other Au(38) clusters reveals that the influence of the ligand on the chiroptical properties is minor.Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au(38)(SCH(2)CH(2)Ph)(24), achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10(-3). Comparison with reported circular dichroism spectra of other Au(38) clusters reveals that the influence of the ligand on the chiroptical properties is minor.
Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au 38 (SCH 2 CH 2 Ph) 24 , achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10 −3 . Comparison with reported circular dichroism spectra of other Au 38 clusters reveals that the influence of the ligand on the chiroptical properties is minor. Clusters of gold atoms protected with achiral thiolates can display chirality, and such chiral nanoparticles could open new possibilities in catalysis and sensing. Here, the first separation of the enantiomers of a gold cluster, protected by achiral thiolates, Au 38 (SCH 2 CH 2 Ph) 24 , is achieved.
Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au(38)(SCH(2)CH(2)Ph)(24), achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10(-3). Comparison with reported circular dichroism spectra of other Au(38) clusters reveals that the influence of the ligand on the chiroptical properties is minor.
Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au38 (SCH2 CH2 Ph)24 , achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10-3 . Comparison with reported circular dichroism spectra of other Au38 clusters reveals that the influence of the ligand on the chiroptical properties is minor.
ArticleNumber 798
Author Knoppe, Stefan
Bürgi, Thomas
Dolamic, Igor
Dass, Amala
Author_xml – sequence: 1
  givenname: Igor
  surname: Dolamic
  fullname: Dolamic, Igor
  organization: Département de Chimie Physique, Université de Genève
– sequence: 2
  givenname: Stefan
  surname: Knoppe
  fullname: Knoppe, Stefan
  organization: Département de Chimie Physique, Université de Genève
– sequence: 3
  givenname: Amala
  surname: Dass
  fullname: Dass, Amala
  organization: Department of Chemistry and Biochemistry, University of Mississippi
– sequence: 4
  givenname: Thomas
  surname: Bürgi
  fullname: Bürgi, Thomas
  email: Thomas.Buergi@unige.ch
  organization: Département de Chimie Physique, Université de Genève
BackLink https://www.ncbi.nlm.nih.gov/pubmed/22531183$$D View this record in MEDLINE/PubMed
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Snippet Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their...
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Anisotropy
Catalysis
Humanities and Social Sciences
Liquid chromatography
multidisciplinary
Optics
Science
Science (multidisciplinary)
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Title First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands
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