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Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport

[Image: see text] Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol–metal bonding. Recent advances in molecular electronics have highlighted this defici...

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Autores principales: Kumar, Sumit, Soni, Saurabh, Danowski, Wojciech, van Beek, Carlijn L. F., Feringa, Ben L., Rudolf, Petra, Chiechi, Ryan C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7472521/
https://www.ncbi.nlm.nih.gov/pubmed/32786759
http://dx.doi.org/10.1021/jacs.0c06508
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author Kumar, Sumit
Soni, Saurabh
Danowski, Wojciech
van Beek, Carlijn L. F.
Feringa, Ben L.
Rudolf, Petra
Chiechi, Ryan C.
author_facet Kumar, Sumit
Soni, Saurabh
Danowski, Wojciech
van Beek, Carlijn L. F.
Feringa, Ben L.
Rudolf, Petra
Chiechi, Ryan C.
author_sort Kumar, Sumit
collection PubMed
description [Image: see text] Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol–metal bonding. Recent advances in molecular electronics have highlighted this deficiency due to the sensitivity of tunneling charge-transport to the subtle differences in the overall composition of SAMs and the chemistry of their attachment to surfaces. These advances have also challenged assumptions about the spontaneous formation of covalent thiol–metal bonds. This paper describes a series of experiments that correlate changes in the physical properties of SAMs to photoelectron spectroscopy to unambiguously assign binding energies of noncovalent interactions to physisorbed disulfides. These disulfides can be converted to covalent metal–thiolate bonds by exposure to free thiols, leading to the remarkable observation of the total loss and recovery of length-dependent tunneling charge-transport. The identification and assignment of physisorbed disulfides solve a long-standing mystery and reveal new, dynamic properties in SAMs of thiols.
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spelling pubmed-74725212020-09-08 Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport Kumar, Sumit Soni, Saurabh Danowski, Wojciech van Beek, Carlijn L. F. Feringa, Ben L. Rudolf, Petra Chiechi, Ryan C. J Am Chem Soc [Image: see text] Despite their ubiquity, self-assembled monolayers (SAMs) of thiols on coinage metals are difficult to study and are still not completely understood, particularly with respect to the nature of thiol–metal bonding. Recent advances in molecular electronics have highlighted this deficiency due to the sensitivity of tunneling charge-transport to the subtle differences in the overall composition of SAMs and the chemistry of their attachment to surfaces. These advances have also challenged assumptions about the spontaneous formation of covalent thiol–metal bonds. This paper describes a series of experiments that correlate changes in the physical properties of SAMs to photoelectron spectroscopy to unambiguously assign binding energies of noncovalent interactions to physisorbed disulfides. These disulfides can be converted to covalent metal–thiolate bonds by exposure to free thiols, leading to the remarkable observation of the total loss and recovery of length-dependent tunneling charge-transport. The identification and assignment of physisorbed disulfides solve a long-standing mystery and reveal new, dynamic properties in SAMs of thiols. American Chemical Society 2020-08-10 2020-09-02 /pmc/articles/PMC7472521/ /pubmed/32786759 http://dx.doi.org/10.1021/jacs.0c06508 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Kumar, Sumit
Soni, Saurabh
Danowski, Wojciech
van Beek, Carlijn L. F.
Feringa, Ben L.
Rudolf, Petra
Chiechi, Ryan C.
Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title_full Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title_fullStr Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title_full_unstemmed Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title_short Correlating the Influence of Disulfides in Monolayers across Photoelectron Spectroscopy Wettability and Tunneling Charge-Transport
title_sort correlating the influence of disulfides in monolayers across photoelectron spectroscopy wettability and tunneling charge-transport
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7472521/
https://www.ncbi.nlm.nih.gov/pubmed/32786759
http://dx.doi.org/10.1021/jacs.0c06508
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