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Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal

Deuteration of a hydrogen bond by replacing protium (H) with deuterium (D) can cause geometric changes in the hydrogen bond, known as the geometric H/D isotope effect (GIE). Understanding the GIEs on global structures and bulk properties is of great importance to study structure–property relationshi...

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Autores principales: Shi, Chao, Zhang, Xi, Yu, Chun-Hua, Yao, Ye-Feng, Zhang, Wen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5797174/
https://www.ncbi.nlm.nih.gov/pubmed/29396512
http://dx.doi.org/10.1038/s41467-018-02931-8
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author Shi, Chao
Zhang, Xi
Yu, Chun-Hua
Yao, Ye-Feng
Zhang, Wen
author_facet Shi, Chao
Zhang, Xi
Yu, Chun-Hua
Yao, Ye-Feng
Zhang, Wen
author_sort Shi, Chao
collection PubMed
description Deuteration of a hydrogen bond by replacing protium (H) with deuterium (D) can cause geometric changes in the hydrogen bond, known as the geometric H/D isotope effect (GIE). Understanding the GIEs on global structures and bulk properties is of great importance to study structure–property relationships of hydrogen-bonded systems. Here, we report a hydrogen-bonded host–guest crystal, imidazolium hydrogen terephthalate, that exemplifies striking GIEs on its hydrogen bonds, phases, and bulk dielectric transition property. Upon deuteration, the donor–acceptor distance in the O–H···O hydrogen bonds in the host structure is found to increase, which results in a change in the global hydrogen-bonded supramolecular structure and the emergence of a new phase (i.e., isotopic polymorphism). Consequently, the dynamics of the confined guest, which depend on the internal pressure exerted by the host framework, are substantially altered, showing a downward shift of the dielectric switching temperature.
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spelling pubmed-57971742018-02-06 Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal Shi, Chao Zhang, Xi Yu, Chun-Hua Yao, Ye-Feng Zhang, Wen Nat Commun Article Deuteration of a hydrogen bond by replacing protium (H) with deuterium (D) can cause geometric changes in the hydrogen bond, known as the geometric H/D isotope effect (GIE). Understanding the GIEs on global structures and bulk properties is of great importance to study structure–property relationships of hydrogen-bonded systems. Here, we report a hydrogen-bonded host–guest crystal, imidazolium hydrogen terephthalate, that exemplifies striking GIEs on its hydrogen bonds, phases, and bulk dielectric transition property. Upon deuteration, the donor–acceptor distance in the O–H···O hydrogen bonds in the host structure is found to increase, which results in a change in the global hydrogen-bonded supramolecular structure and the emergence of a new phase (i.e., isotopic polymorphism). Consequently, the dynamics of the confined guest, which depend on the internal pressure exerted by the host framework, are substantially altered, showing a downward shift of the dielectric switching temperature. Nature Publishing Group UK 2018-02-02 /pmc/articles/PMC5797174/ /pubmed/29396512 http://dx.doi.org/10.1038/s41467-018-02931-8 Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Shi, Chao
Zhang, Xi
Yu, Chun-Hua
Yao, Ye-Feng
Zhang, Wen
Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title_full Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title_fullStr Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title_full_unstemmed Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title_short Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
title_sort geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5797174/
https://www.ncbi.nlm.nih.gov/pubmed/29396512
http://dx.doi.org/10.1038/s41467-018-02931-8
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