Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments
The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct pro...
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Nature Publishing Group
2015
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| Online Access: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4682163/ |
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pubmed-46821632015-12-29 Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments Lissau, Henriette Frisenda, Riccardo Olsen, Stine T. Jevric, Martyn Parker, Christian R. Kadziola, Anders Hansen, Thorsten van der Zant, Herre S. J. Brøndsted Nielsen, Mogens Mikkelsen, Kurt V. Article The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment. Nature Publishing Group 2015-12-15 /pmc/articles/PMC4682163/ /pubmed/26667583 http://dx.doi.org/10.1038/ncomms10233 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/ |
| repository_type |
Open Access Journal |
| institution_category |
Foreign Institution |
| institution |
US National Center for Biotechnology Information |
| building |
NCBI PubMed |
| collection |
Online Access |
| language |
English |
| format |
Online |
| author |
Lissau, Henriette Frisenda, Riccardo Olsen, Stine T. Jevric, Martyn Parker, Christian R. Kadziola, Anders Hansen, Thorsten van der Zant, Herre S. J. Brøndsted Nielsen, Mogens Mikkelsen, Kurt V. |
| spellingShingle |
Lissau, Henriette Frisenda, Riccardo Olsen, Stine T. Jevric, Martyn Parker, Christian R. Kadziola, Anders Hansen, Thorsten van der Zant, Herre S. J. Brøndsted Nielsen, Mogens Mikkelsen, Kurt V. Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| author_facet |
Lissau, Henriette Frisenda, Riccardo Olsen, Stine T. Jevric, Martyn Parker, Christian R. Kadziola, Anders Hansen, Thorsten van der Zant, Herre S. J. Brøndsted Nielsen, Mogens Mikkelsen, Kurt V. |
| author_sort |
Lissau, Henriette |
| title |
Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| title_short |
Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| title_full |
Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| title_fullStr |
Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| title_full_unstemmed |
Tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| title_sort |
tracking molecular resonance forms of donor–acceptor push–pull molecules by single-molecule conductance experiments |
| description |
The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment. |
| publisher |
Nature Publishing Group |
| publishDate |
2015 |
| url |
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4682163/ |
| _version_ |
1613513722716749824 |