Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks

Marshall, R. J., McGuire, J., Wilson, C. and Forgan, R. S. (2018) Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks. Supramolecular Chemistry, 30(9), pp. 732-741. (doi: 10.1080/10610278.2017.1370095)

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Introduction of hydrogen bond functionality into metal-organic frameworks can enhance guest binding and activation, but a combination of linker flexibility and interligand hydrogen bonding often results in the generation of unwanted structures where the functionality is masked. Herein, we describe the self-assembly of three materials, where Cd2+, Ca2+, and Zn2+ are linked by N,Nʹ-bis(4-carboxyphenyl)urea, and examine the effect of the urea units on structure formation, the generation of unusual secondary building units, structural flexibility, and guest binding. The flexibility of the Zn MOF is probed through single-crystal to single-crystal transformations upon exchange of DMF guests for CS2, showing that the lability of the [Zn4O(RCO2)6] cluster towards solvation enables the urea linkers to adopt distorted conformations as the MOF breathes, even facilitating rotation from the trans/trans to the trans/cis conformation without compromising the overall topology. The results have significant implications in the mechanistic understanding of the hydrolytic stability of MOFs, and in preparing heterogeneous organocatalysts.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Forgan, Professor Ross and McGuire, Mr Jake and Wilson, Dr Claire and Marshall, Mr Ross James
Authors: Marshall, R. J., McGuire, J., Wilson, C., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Supramolecular Chemistry
Publisher:Taylor & Francis
ISSN (Online):1029-0478
Published Online:01 September 2017
Copyright Holders:Copyright © 2017 The Authors
First Published:First published in Supramolecular Chemistry 30(9):732-741
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 and Physical Sciences Research Council (EPSRC)EP/L004461/1CHEM - CHEMISTRY