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The effect of pressure on the post-synthetic modification of a nanoporous metal-organic framework

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c3nr04161a_1_.pdf (843.1Kb)
Date
04/2014
Author
McKellar, Scott C.
Graham, Alexander J.
Allan, David R.
Haja Mohideen, Mohamed Infas
Morris, Russell Edward
Moggach, Stephen A.
Keywords
Carbon-dioxide capture
Pore-size
Adsorption
Phase
QD Chemistry
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Abstract
Here we report four post-synthetic modifications, including the first ever example of a high pressure-induced post-synthetic modification, of a porous copper-based metal-organic framework. Ligand exchange with a water ligand at the axial metal site occurs with methanol, acetonitrile, methylamine and ethylamine within a single-crystal and without the need to expose a free metal site prior to modification, resulting in significant changes in the pore size, shape and functionality. Pressure experiments carried out using isopropylalcohol and acetaldehyde, however, results in no ligand exchange. By using these solvents as hydrostatic media for high-pressure single-crystal X-ray diffraction experiments, we have investigated the effect of ligand exchange on the stability and compressibility of the framework and demonstrate that post-synthetic ligand exchange is very sensitive to both the molecular size and functionality of the exchanged ligand. We also demonstrate the ability to force hydrophilic molecules into hydrophobic pores using high pressures which results in a pressure-induced chemical decomposition of the Cu-framework.
Citation
McKellar , S C , Graham , A J , Allan , D R , Haja Mohideen , M I , Morris , R E & Moggach , S A 2014 , ' The effect of pressure on the post-synthetic modification of a nanoporous metal-organic framework ' , Nanoscale , vol. 6 , no. 8 , pp. 4163-4173 . https://doi.org/10.1039/c3nr04161a
Publication
Nanoscale
Status
Peer reviewed
DOI
https://doi.org/10.1039/c3nr04161a
ISSN
2040-3364
Type
Journal article
Rights
(c) 2014 the authors and Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Description
This work is supported by funding from the EPSRC UK and the Leverhulme Trust
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/7420

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