Sussardi, A., Hobday, C. L., Marshall, R. J., Forgan, R. S. , Jones, A. C. and Moggach, S. A. (2020) Correlating pressure-induced emission modulation with linker rotation in a photoluminescent MOF. Angewandte Chemie (International Edition), 59(21), pp. 8118-8122. (doi: 10.1002/anie.202000555) (PMID:32133755) (PMCID:PMC7317771)
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Abstract
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 study 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.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Forgan, Professor Ross and Marshall, Mr Ross James |
| Authors: | Sussardi, A., Hobday, C. L., Marshall, R. J., Forgan, R. S., Jones, A. C., and Moggach, S. A. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Angewandte Chemie (International Edition) |
| Publisher: | Wiley |
| ISSN: | 1433-7851 |
| ISSN (Online): | 1521-3773 |
| Published Online: | 04 March 2020 |
| Copyright Holders: | Copyright © 2020 The Authors |
| First Published: | First published in Angewandte Chemie (International Edition) 59(21): 8118-8122 |
| Publisher Policy: | Reproduced under a Creative Commons licence |
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