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Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding

Direct spectroscopic evidence for hydrogen‐bonded clusters of like‐charged ions is reported for ionic liquids. The measured infrared O−H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion‐corrected DFT calculated frequencies of linear and cyclic clusters. C...

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Autores principales: Knorr, Anne, Stange, Peter, Fumino, Koichi, Weinhold, Frank, Ludwig, Ralf
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4819523/
https://www.ncbi.nlm.nih.gov/pubmed/26670942
http://dx.doi.org/10.1002/cphc.201501134
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author Knorr, Anne
Stange, Peter
Fumino, Koichi
Weinhold, Frank
Ludwig, Ralf
author_facet Knorr, Anne
Stange, Peter
Fumino, Koichi
Weinhold, Frank
Ludwig, Ralf
author_sort Knorr, Anne
collection PubMed
description Direct spectroscopic evidence for hydrogen‐bonded clusters of like‐charged ions is reported for ionic liquids. The measured infrared O−H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion‐corrected DFT calculated frequencies of linear and cyclic clusters. Compensating the like‐charge Coulomb repulsion, these cationic clusters can range up to cyclic tetramers resembling molecular clusters of water and alcohols. These ionic clusters are mainly present at low temperature and show strong cooperative effects in hydrogen bonding. DFT‐D3 calculations of the pure multiply charged clusters suggest that the attractive hydrogen bonds can compete with repulsive Coulomb forces.
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spelling pubmed-48195232016-04-28 Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding Knorr, Anne Stange, Peter Fumino, Koichi Weinhold, Frank Ludwig, Ralf Chemphyschem Communications Direct spectroscopic evidence for hydrogen‐bonded clusters of like‐charged ions is reported for ionic liquids. The measured infrared O−H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion‐corrected DFT calculated frequencies of linear and cyclic clusters. Compensating the like‐charge Coulomb repulsion, these cationic clusters can range up to cyclic tetramers resembling molecular clusters of water and alcohols. These ionic clusters are mainly present at low temperature and show strong cooperative effects in hydrogen bonding. DFT‐D3 calculations of the pure multiply charged clusters suggest that the attractive hydrogen bonds can compete with repulsive Coulomb forces. John Wiley and Sons Inc. 2016-01-08 2016-02 /pmc/articles/PMC4819523/ /pubmed/26670942 http://dx.doi.org/10.1002/cphc.201501134 Text en © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial (http://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Communications
Knorr, Anne
Stange, Peter
Fumino, Koichi
Weinhold, Frank
Ludwig, Ralf
Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title_full Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title_fullStr Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title_full_unstemmed Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title_short Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
title_sort spectroscopic evidence for clusters of like‐charged ions in ionic liquids stabilized by cooperative hydrogen bonding
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4819523/
https://www.ncbi.nlm.nih.gov/pubmed/26670942
http://dx.doi.org/10.1002/cphc.201501134
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