Stereoselective halogenation of integral unsaturated C-C bonds in chemically and mechanically robust Zr and Hf MOFs

Marshall, R. J., Griffin, S. L., Wilson, C. and Forgan, R. S. (2016) Stereoselective halogenation of integral unsaturated C-C bonds in chemically and mechanically robust Zr and Hf MOFs. Chemistry: A European Journal, 22(14), pp. 4870-4877. (doi:10.1002/chem.201505185) (PMID:26916707)

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Abstract

Metal–organic frameworks (MOFs) containing ZrIV-based secondary building units (SBUs), as in the UiO-66 series, are receiving widespread research interest due to their enhanced chemical and mechanical stabilities. We report the synthesis and extensive characterisation, as both bulk microcrystalline and single crystal forms, of extended UiO-66 (Zr and Hf) series MOFs containing integral unsaturated alkene, alkyne and butadiyne units, which serve as reactive sites for postsynthetic modification (PSM) by halogenation. The water stability of a Zr–stilbene MOF allows the dual insertion of both −OH and −Br groups in a single, aqueous bromohydrination step. Quantitative bromination of alkyne- and butadiyne-containing MOFs is demonstrated to be stereoselective, as a consequence of the linker geometry when bound in the MOFs, while the inherent change in hybridisation and geometry of integral linker atoms is facilitated by the high mechanical stabilities of the MOFs, allowing bromination to be characterised in a single-crystal to single-crystal (SCSC) manner. The facile addition of bromine across the unsaturated C−C bonds in the MOFs in solution is extended to irreversible iodine sequestration in the vapour phase. A large-pore interpenetrated Zr MOF demonstrates an I2 storage capacity of 279 % w/w, through a combination of chemisorption and physisorption, which is comparable to the highest reported capacities of benchmark iodine storage materials for radioactive I2 sequestration. We expect this facile PSM process to not only allow trapping of toxic vapours, but also modulate the mechanical properties of the MOFs.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Dr Claire and Forgan, Dr Ross and Marshall, Mr Ross James
Authors: Marshall, R. J., Griffin, S. L., Wilson, C., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Publisher:WILEY-VCH Verlag GmbH & Co. KGaA
ISSN:0947-6539
ISSN (Online):1521-3765
Published Online:24 February 2016
Copyright Holders:Copyright © 2016 The Authors
First Published:First published in Chemistry: A European Journal 22(14):4870-4877
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