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Unpicking the determinants of amide NH••O=C hydrogen bond strength with diphenylacetylene molecular balances

Unpicking the determinants of amide NH••O=C hydrogen bond strength with diphenylacetylene molecular balances
Unpicking the determinants of amide NH••O=C hydrogen bond strength with diphenylacetylene molecular balances
Hydrogen bonding plays an essential part in dictating the properties of natural and synthetic materials. Secondary amides are well suited to cross–strand interactions through the display of both hydrogen bond donors and acceptors and are prevalent in polymers such as proteins, nylon, and Kevlar(TM). In attempting to measure hydrogen bond strength and to delineate the stereoelectronic components of the interaction, context frequently becomes vitally important. This makes molecular balances – systems in which direct comparison of two groups is possible – an appealing bottom up approach that allows the complexity of larger systems to be stripped away. We have previously reported a family of single molecule conformational switches that are responsive to diverse stimuli including Brønsted and Lewis acids, anions, and redox gradients. In this work we assess the ability of the scaffold, based on a 2,6-disubstituted diphenylacetylene, to measure accurately the difference in hydrogen bond strength between variously functionalised amides. In all of the examples investigated hydrogen bond strength closely correlate to measures of Brønstead acidity suggesting that the scaffold is well-suited as a platform for the accurate determination of bond strength in variously substituted systems.
1477-0520
Luccarelli, James
9afdfaf8-5c48-4110-a281-2eeeabb6c2ff
Jones, Ian M.
3d141d56-9e92-4ebc-bd47-c248d83dac66
Thompson, Sam
99b7e34e-fe24-401c-b7b0-64e56cbbbcb1
Hamilton, Andrew D.
048a6c75-91bf-4555-ab12-ce885eee65dd
Luccarelli, James
9afdfaf8-5c48-4110-a281-2eeeabb6c2ff
Jones, Ian M.
3d141d56-9e92-4ebc-bd47-c248d83dac66
Thompson, Sam
99b7e34e-fe24-401c-b7b0-64e56cbbbcb1
Hamilton, Andrew D.
048a6c75-91bf-4555-ab12-ce885eee65dd

Luccarelli, James, Jones, Ian M., Thompson, Sam and Hamilton, Andrew D. (2017) Unpicking the determinants of amide NH••O=C hydrogen bond strength with diphenylacetylene molecular balances. Organic & Biomolecular Chemistry. (doi:10.1039/C7OB02026K).

Record type: Article

Abstract

Hydrogen bonding plays an essential part in dictating the properties of natural and synthetic materials. Secondary amides are well suited to cross–strand interactions through the display of both hydrogen bond donors and acceptors and are prevalent in polymers such as proteins, nylon, and Kevlar(TM). In attempting to measure hydrogen bond strength and to delineate the stereoelectronic components of the interaction, context frequently becomes vitally important. This makes molecular balances – systems in which direct comparison of two groups is possible – an appealing bottom up approach that allows the complexity of larger systems to be stripped away. We have previously reported a family of single molecule conformational switches that are responsive to diverse stimuli including Brønsted and Lewis acids, anions, and redox gradients. In this work we assess the ability of the scaffold, based on a 2,6-disubstituted diphenylacetylene, to measure accurately the difference in hydrogen bond strength between variously functionalised amides. In all of the examples investigated hydrogen bond strength closely correlate to measures of Brønstead acidity suggesting that the scaffold is well-suited as a platform for the accurate determination of bond strength in variously substituted systems.

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2017 obc c7ob02026k - Accepted Manuscript
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Accepted/In Press date: 27 September 2017
e-pub ahead of print date: 27 September 2017

Identifiers

Local EPrints ID: 415020
URI: http://eprints.soton.ac.uk/id/eprint/415020
ISSN: 1477-0520
PURE UUID: c46c1ac5-f322-482b-8996-396581314097
ORCID for Sam Thompson: ORCID iD orcid.org/0000-0001-6267-5693

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Date deposited: 20 Oct 2017 16:31
Last modified: 16 Mar 2024 05:47

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Contributors

Author: James Luccarelli
Author: Ian M. Jones
Author: Sam Thompson ORCID iD
Author: Andrew D. Hamilton

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