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Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism

The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule...

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Autores principales: Dolamic, Igor, Varnholt, Birte, Bürgi, Thomas
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Pub. Group 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4432620/
https://www.ncbi.nlm.nih.gov/pubmed/25960309
http://dx.doi.org/10.1038/ncomms8117
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author Dolamic, Igor
Varnholt, Birte
Bürgi, Thomas
author_facet Dolamic, Igor
Varnholt, Birte
Bürgi, Thomas
author_sort Dolamic, Igor
collection PubMed
description The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au(38)(2-PET)(24) (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis.
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spelling pubmed-44326202015-05-23 Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism Dolamic, Igor Varnholt, Birte Bürgi, Thomas Nat Commun Article The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au(38)(2-PET)(24) (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis. Nature Pub. Group 2015-05-11 /pmc/articles/PMC4432620/ /pubmed/25960309 http://dx.doi.org/10.1038/ncomms8117 Text en Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Dolamic, Igor
Varnholt, Birte
Bürgi, Thomas
Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title_full Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title_fullStr Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title_full_unstemmed Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title_short Chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
title_sort chirality transfer from gold nanocluster to adsorbate evidenced by vibrational circular dichroism
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4432620/
https://www.ncbi.nlm.nih.gov/pubmed/25960309
http://dx.doi.org/10.1038/ncomms8117
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