Measuring the mechanical properties of molecular conformers

Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has no...

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Main Authors: Jarvis, Samuel Paul, Taylor, Simon, Baran, J.D., Champness, Neil R., Larsson, J.A., Moriarty, Philip
Format: Article
Published: Nature Publishing Group 2015
Online Access:https://eprints.nottingham.ac.uk/31737/
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author Jarvis, Samuel Paul
Taylor, Simon
Baran, J.D.
Champness, Neil R.
Larsson, J.A.
Moriarty, Philip
author_facet Jarvis, Samuel Paul
Taylor, Simon
Baran, J.D.
Champness, Neil R.
Larsson, J.A.
Moriarty, Philip
author_sort Jarvis, Samuel Paul
building Nottingham Research Data Repository
collection Online Access
description Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.
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spelling nottingham-317372020-05-04T17:16:38Z https://eprints.nottingham.ac.uk/31737/ Measuring the mechanical properties of molecular conformers Jarvis, Samuel Paul Taylor, Simon Baran, J.D. Champness, Neil R. Larsson, J.A. Moriarty, Philip Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules. Nature Publishing Group 2015-09-21 Article PeerReviewed Jarvis, Samuel Paul, Taylor, Simon, Baran, J.D., Champness, Neil R., Larsson, J.A. and Moriarty, Philip (2015) Measuring the mechanical properties of molecular conformers. Nature Communications, 6 (8338). pp. 1-7. ISSN 2041-1723 http://www.nature.com/ncomms/2015/150921/ncomms9338/full/ncomms9338.html doi:10.1038/ncomms9338 doi:10.1038/ncomms9338
spellingShingle Jarvis, Samuel Paul
Taylor, Simon
Baran, J.D.
Champness, Neil R.
Larsson, J.A.
Moriarty, Philip
Measuring the mechanical properties of molecular conformers
title Measuring the mechanical properties of molecular conformers
title_full Measuring the mechanical properties of molecular conformers
title_fullStr Measuring the mechanical properties of molecular conformers
title_full_unstemmed Measuring the mechanical properties of molecular conformers
title_short Measuring the mechanical properties of molecular conformers
title_sort measuring the mechanical properties of molecular conformers
url https://eprints.nottingham.ac.uk/31737/
https://eprints.nottingham.ac.uk/31737/
https://eprints.nottingham.ac.uk/31737/