Issue 8, 2014

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

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.

Graphical abstract: The effect of pressure on the post-synthetic modification of a nanoporous metal–organic framework

Supplementary files

Article information

Article type
Paper
Submitted
07 Aug 2013
Accepted
21 Feb 2014
First published
24 Feb 2014
This article is Open Access
Creative Commons BY license

Nanoscale, 2014,6, 4163-4173

Author version available

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

S. C. McKellar, A. J. Graham, D. R. Allan, M. I. H. Mohideen, R. E. Morris and S. A. Moggach, Nanoscale, 2014, 6, 4163 DOI: 10.1039/C3NR04161A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements