Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy

The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational sp...

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Autores: Ma, Jiarui, Insausti, Aran, Al-Jabiri, Mohamad H., Carlson, Colton D., Jäger, Wolfgang, Xu, Yunjie
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/364303
Acceso en línea:http://hdl.handle.net/10261/364303
Access Level:acceso abierto
Palabra clave:Density functional theory
Rotational spectra
Molecular structure
Conformational isomerism
Molecular beam Fourier-transform microwave spectroscopy
Rotational spectroscopy
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spelling Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopyMa, JiaruiInsausti, AranAl-Jabiri, Mohamad H.Carlson, Colton D.Jäger, WolfgangXu, YunjieDensity functional theoryRotational spectraMolecular structureConformational isomerismMolecular beam Fourier-transform microwave spectroscopyRotational spectroscopyThe conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C–O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds.This work was funded by the Natural Sciences and Engineering Research Council of Canada and the University of Alberta.Peer reviewedAIP PublishingNatural Sciences and Engineering Research Council of CanadaUniversity of AlbertaInsausti, Aran [0000-0002-9291-1762]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/364303reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)InglésThe underlying dataset has been published as supplementary material of the article in the publisher platform at https://doi.org/10.1063/5.0203123https://doi.org/10.1063/5.0203123Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3643032026-05-22T06:33:51Z
dc.title.none.fl_str_mv Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
title Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
spellingShingle Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
Ma, Jiarui
Density functional theory
Rotational spectra
Molecular structure
Conformational isomerism
Molecular beam Fourier-transform microwave spectroscopy
Rotational spectroscopy
title_short Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
title_full Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
title_fullStr Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
title_full_unstemmed Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
title_sort Unlocking a new hydrogen-bonding marker: C–O bond shortening in vicinal diols revealed by rotational spectroscopy
dc.creator.none.fl_str_mv Ma, Jiarui
Insausti, Aran
Al-Jabiri, Mohamad H.
Carlson, Colton D.
Jäger, Wolfgang
Xu, Yunjie
author Ma, Jiarui
author_facet Ma, Jiarui
Insausti, Aran
Al-Jabiri, Mohamad H.
Carlson, Colton D.
Jäger, Wolfgang
Xu, Yunjie
author_role author
author2 Insausti, Aran
Al-Jabiri, Mohamad H.
Carlson, Colton D.
Jäger, Wolfgang
Xu, Yunjie
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Natural Sciences and Engineering Research Council of Canada
University of Alberta
Insausti, Aran [0000-0002-9291-1762]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Density functional theory
Rotational spectra
Molecular structure
Conformational isomerism
Molecular beam Fourier-transform microwave spectroscopy
Rotational spectroscopy
topic Density functional theory
Rotational spectra
Molecular structure
Conformational isomerism
Molecular beam Fourier-transform microwave spectroscopy
Rotational spectroscopy
description The conformational space of cis-1,2-cyclohexanediol, a model molecule for cyclic vicinal diols, was investigated using rotational spectroscopy and density functional theory calculations. Four low energy conformers within an energy window of 5 kJ mol−1 were identified computationally. A rotational spectrum of jet-cooled cis-1,2-cyclohexanediol was recorded with a chirped pulse Fourier transform microwave spectrometer. Two sets of rotational transitions were observed and could be assigned to conformers of cis-1,2-cyclohexanediol. The non-observation of other low energy conformers was explained by conformational conversion barrier height calculations and results from experimental spectra recorded with different carrier gases. Eight isotopologues, including those with 13C and 18O, of the lowest energy conformer were observed, allowing the determination of the semi-experimental equilibrium structure, reSE. Interestingly, the structural analysis revealed that the C–O bond length of the intramolecular hydrogen-bond donor is shorter than that of the acceptor. This appears to be a general characteristic of vicinal diols and can be used as a novel hydrogen-bond marker in such compounds.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/364303
url http://hdl.handle.net/10261/364303
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv The underlying dataset has been published as supplementary material of the article in the publisher platform at https://doi.org/10.1063/5.0203123
https://doi.org/10.1063/5.0203123
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv AIP Publishing
publisher.none.fl_str_mv AIP Publishing
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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