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Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF
Conformational changes of linker units in metal‐organic frameworks (MOFs) are often responsible for gate‐opening phenomena in selective gas adsorption and stimuli‐responsive optical and electrical sensing behaviour. Herein, we show that pressure‐induced bathochromic shifts in both fluorescence emiss...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7317771/ https://www.ncbi.nlm.nih.gov/pubmed/32133755 http://dx.doi.org/10.1002/anie.202000555 |
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author | Sussardi, Alif Hobday, Claire L. Marshall, Ross J. Forgan, Ross S. Jones, Anita C. Moggach, Stephen A. |
author_facet | Sussardi, Alif Hobday, Claire L. Marshall, Ross J. Forgan, Ross S. Jones, Anita C. Moggach, Stephen A. |
author_sort | Sussardi, Alif |
collection | PubMed |
description | Conformational changes of linker units in metal‐organic frameworks (MOFs) are often responsible for gate‐opening phenomena in selective gas adsorption and stimuli‐responsive optical and electrical sensing behaviour. Herein, we show that pressure‐induced bathochromic shifts in both fluorescence emission and UV/Vis absorption spectra of a two‐fold interpenetrated Hf MOF, linked by 1,4‐phenylene‐bis(4‐ethynylbenzoate) ligands (Hf‐peb), are induced by rotation of the central phenyl ring of the linker, from a coplanar arrangement to a twisted, previously unseen conformer. Single‐crystal X‐ray diffraction, alongside in situ fluorescence and UV/Vis absorption spectroscopies, measured up to 2.1 GPa in a diamond anvil cell on single crystals, are in excellent agreement, correlating linker rotation with modulation of emission. Topologically isolating the 1,4‐phenylene‐bis(4‐ethynylbenzoate) units within a MOF facilitates concurrent structural and spectroscopic studies in the absence of intermolecular perturbation, allowing characterisation of the luminescence properties of a high‐energy, twisted conformation of the previously well‐studied chromophore. We expect the unique environment provided by network solids, and the capability of combining crystallographic and spectroscopic analysis, will greatly enhance understanding of luminescent molecules and lead to the development of novel sensors and adsorbents. |
format | Online Article Text |
id | pubmed-7317771 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-73177712020-06-29 Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF Sussardi, Alif Hobday, Claire L. Marshall, Ross J. Forgan, Ross S. Jones, Anita C. Moggach, Stephen A. Angew Chem Int Ed Engl Communications Conformational changes of linker units in metal‐organic frameworks (MOFs) are often responsible for gate‐opening phenomena in selective gas adsorption and stimuli‐responsive optical and electrical sensing behaviour. Herein, we show that pressure‐induced bathochromic shifts in both fluorescence emission and UV/Vis absorption spectra of a two‐fold interpenetrated Hf MOF, linked by 1,4‐phenylene‐bis(4‐ethynylbenzoate) ligands (Hf‐peb), are induced by rotation of the central phenyl ring of the linker, from a coplanar arrangement to a twisted, previously unseen conformer. Single‐crystal X‐ray diffraction, alongside in situ fluorescence and UV/Vis absorption spectroscopies, measured up to 2.1 GPa in a diamond anvil cell on single crystals, are in excellent agreement, correlating linker rotation with modulation of emission. Topologically isolating the 1,4‐phenylene‐bis(4‐ethynylbenzoate) units within a MOF facilitates concurrent structural and spectroscopic studies in the absence of intermolecular perturbation, allowing characterisation of the luminescence properties of a high‐energy, twisted conformation of the previously well‐studied chromophore. We expect the unique environment provided by network solids, and the capability of combining crystallographic and spectroscopic analysis, will greatly enhance understanding of luminescent molecules and lead to the development of novel sensors and adsorbents. John Wiley and Sons Inc. 2020-03-17 2020-05-18 /pmc/articles/PMC7317771/ /pubmed/32133755 http://dx.doi.org/10.1002/anie.202000555 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Sussardi, Alif Hobday, Claire L. Marshall, Ross J. Forgan, Ross S. Jones, Anita C. Moggach, Stephen A. Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title | Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title_full | Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title_fullStr | Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title_full_unstemmed | Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title_short | Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF |
title_sort | correlating pressure‐induced emission modulation with linker rotation in a photoluminescent mof |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7317771/ https://www.ncbi.nlm.nih.gov/pubmed/32133755 http://dx.doi.org/10.1002/anie.202000555 |
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