Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents

Voltammetric experiments with 9,10-anthraquinone and 1,4-benzoquinone performed under controlled moisture conditions indicate that the hydrogen-bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔEpred=|Epred(1)−Epred(2)|, which is the poten...

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Main Authors: Lee, Melvyn, Hirao, Hajime, Webster, Richard D., Tessensohn, Malcolm E.
Other Authors: School of Physical and Mathematical Sciences
Format: Journal Article
Language:English
Published: 2015
Subjects:
Online Access:https://hdl.handle.net/10356/103936
http://hdl.handle.net/10220/24612
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author Lee, Melvyn
Hirao, Hajime
Webster, Richard D.
Tessensohn, Malcolm E.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Lee, Melvyn
Hirao, Hajime
Webster, Richard D.
Tessensohn, Malcolm E.
author_sort Lee, Melvyn
collection NTU
description Voltammetric experiments with 9,10-anthraquinone and 1,4-benzoquinone performed under controlled moisture conditions indicate that the hydrogen-bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔEpred=|Epred(1)−Epred(2)|, which is the potential separation between the two one-electron reduction processes. This electrochemical parameter is inversely related to the strength of the interactions and can be used to differentiate between primary, secondary, tertiary alcohols, and even diols, as it is sensitive to both their steric and electronic properties. The results are highly reproducible across two solvents with substantially different hydrogen-bonding properties (CH3CN and CH2Cl2) and are supported by density functional theory calculations. This indicates that the numerous solvent–alcohol interactions are less significant than the quinone–alcohol hydrogen-bonding interactions. The utility of ΔEpred was illustrated by comparisons between 1) 3,3,3-trifluoro-n-propanol and 1,3-difluoroisopropanol and 2) ethylene glycol and 2,2,2-trifluoroethanol.
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spelling ntu-10356/1039362020-03-07T12:34:53Z Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents Lee, Melvyn Hirao, Hajime Webster, Richard D. Tessensohn, Malcolm E. School of Physical and Mathematical Sciences DRNTU::Science::Physics Voltammetric experiments with 9,10-anthraquinone and 1,4-benzoquinone performed under controlled moisture conditions indicate that the hydrogen-bond strengths of alcohols in aprotic organic solvents can be differentiated by the electrochemical parameter ΔEpred=|Epred(1)−Epred(2)|, which is the potential separation between the two one-electron reduction processes. This electrochemical parameter is inversely related to the strength of the interactions and can be used to differentiate between primary, secondary, tertiary alcohols, and even diols, as it is sensitive to both their steric and electronic properties. The results are highly reproducible across two solvents with substantially different hydrogen-bonding properties (CH3CN and CH2Cl2) and are supported by density functional theory calculations. This indicates that the numerous solvent–alcohol interactions are less significant than the quinone–alcohol hydrogen-bonding interactions. The utility of ΔEpred was illustrated by comparisons between 1) 3,3,3-trifluoro-n-propanol and 1,3-difluoroisopropanol and 2) ethylene glycol and 2,2,2-trifluoroethanol. 2015-01-14T08:18:56Z 2019-12-06T21:23:21Z 2015-01-14T08:18:56Z 2019-12-06T21:23:21Z 2015 2015 Journal Article Tessensohn, M. E., Lee, M., Hirao, H., & Webster, R. D. (2015). Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents. ChemPhysChem, 16(1), 160-168. 1439-4235 https://hdl.handle.net/10356/103936 http://hdl.handle.net/10220/24612 10.1002/cphc.201402693 en ChemPhysChem © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
spellingShingle DRNTU::Science::Physics
Lee, Melvyn
Hirao, Hajime
Webster, Richard D.
Tessensohn, Malcolm E.
Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title_full Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title_fullStr Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title_full_unstemmed Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title_short Measuring the relative hydrogen-bonding strengths of alcohols in aprotic organic solvents
title_sort measuring the relative hydrogen bonding strengths of alcohols in aprotic organic solvents
topic DRNTU::Science::Physics
url https://hdl.handle.net/10356/103936
http://hdl.handle.net/10220/24612
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