Functional versatility of a series of Zr metal-organic frameworks probed by solid-state photoluminescence spectroscopy

Marshall, R. J., Kalinovskyy, Y., Griffin, S. L., Wilson, C. , Blight, B. A. and Forgan, R. S. (2017) Functional versatility of a series of Zr metal-organic frameworks probed by solid-state photoluminescence spectroscopy. Journal of the American Chemical Society, 139(17), pp. 6253-6260. (doi:10.1021/jacs.7b02184) (PMID:28385019)

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Abstract

Many of the desirable properties of metal-organic frameworks (MOFs) can be tuned by chemical functionalization of the organic ligands that connect their metal clusters into multidimensional network solids. When these linker molecules are intrinsically fluorescent, they can pass on this property to the resultant MOF, potentially generating solid-state sensors, as analytes can be bound within their porous interiors. Herein, we report the synthesis of a series of 14 interpenetrated Zr and Hf MOFs linked by functionalized 4,4ʹ-[1,4-phenylene-bis(ethyne-2,1-diyl)]-dibenzoate (peb2-) ligands, and analyse the effect of functional group incorporation on their structures and properties. Addition of methyl, fluoro, naphthyl and benzothiadiazolyl units does not affect the underlying topology, but induces subtle structural changes, such as ligand rotation, and mediates host-guest interactions. Further, we demonstrate that solid-state photoluminescence spectroscopy can be used to probe these effects. For instance, introduction of naphthyl and benzothiadiazolyl units yields MOFs that can act as stable fluorescent water sensors, a dimethyl modified MOF exhibits a temperature dependent phase change controlled by steric clashes between interpenetrated nets, and a tetrafluorinated analogue is found to be superhydrophobic despite only partial fluorination of its organic backbone. These subtle changes in ligand structure coupled with the consistent framework topology give rise to a series of MOFs with a remarkable range of physical properties that are not observed with the ligands alone.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Dr Claire and Forgan, Dr Ross and Griffin, Miss Sarah and Marshall, Mr Ross James
Authors: Marshall, R. J., Kalinovskyy, Y., Griffin, S. L., Wilson, C., Blight, B. A., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:07 April 2017
Copyright Holders:Copyright © 2017 American Chemical Society
First Published:First published in Journal of the American Chemical Society 139(17):6253-6260
Publisher Policy:Reproduced under a Creative Commons License
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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
619471Biomimetic guest selective metal-organic frameworks: catalysis and self-assemblyRoss ForganEngineering & Physical Sciences Research Council (EPSRC)EP/L004461/1CHEM - CHEMISTRY