Single-crystal to single-crystal mechanical contraction of metal-organic frameworks through stereoselective post-synthetic bromination

Marshall, R. J., Griffin, S. L., Wilson, C. and Forgan, R. S. (2015) Single-crystal to single-crystal mechanical contraction of metal-organic frameworks through stereoselective post-synthetic bromination. Journal of the American Chemical Society, 137(30), pp. 9527-9530. (doi:10.1021/jacs.5b05434) (PMID:26175317)

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Abstract

The properties of metal-organic frameworks (MOFs) can be tuned by post-synthetic modification (PSM) to introduce specific functionalities after their synthesis. Typically, PSM is carried out on pendant functional groups or through metal/ligand exchange, preserving the structure of the MOF. We report herein the bromination of integral alkyne units in a pair of Zr4+ and Hf4+ MOFs, which proceeds stereoselectively in a single-crystal to single-crystal manner. The chemical and mechanical changes in the MOFs are ex-tensively characterised, including the crystal structures of the post-synthetically brominated materials, which show a mechanical contraction of up to 3.7% in volume. The combination of stability and chemical reactivity in these MOFs leads to the possibility of tuning mechanical properties by chemical transformation, while also opening up new routes to internal pore functionalization.

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:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Copyright Holders:Copyright © 2015 American Chemical Society
First Published:First published in Journal of the American Chemical Society 137(30):9527-9530
Publisher Policy:Reproduced under a Creative Commons License
Data DOI:10.5525/gla.researchdata.200

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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