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

DOI: 10.1039/C3NR04161A DOI Help

Authors: Scott Mckellar (University of Edinburgh) , Alexander J. Graham (University of Edinburgh) , Dave Allan (Diamond Light Source) , M. Infas H. Mohideen (University of St Andrews) , Russell E Morris (University of St Andrews) , Stephen Moggach (The University of Edinburgh)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nanoscale , VOL 6 , PAGES 4163 - 4173

State: Published (Approved)
Published: February 2014

Open Access Open Access

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.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction