High-resolution solid-state super(13)C NMR spectroscopy of the paramagnetic metal-organic frameworks, STAM-1 and HKUST-1

Solid-state super(13)C magic-angle spinning (MAS) NMR spectroscopy is used to investigate the structure of the Cu(ii)-based metal-organic frameworks (MOFs), HKUST-1 and STAM-1, and the structural changes occurring within these MOFs upon activation (dehydration). NMR spectroscopy is an attractive tec...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2012-12, Vol.15 (3), p.919-929
Main Authors: Dawson, Daniel M, Jamieson, Lauren E, Mohideen, MInfas H, McKinlay, Alistair C, Smellie, Iain A, Cadou, Romain, Keddie, Neil S, Morris, Russell E, Ashbrook, Sharon E
Format: Article
Language:English
Subjects:
Acquisitions
Activation
Labelling
Marketing
Metal-organic frameworks
NMR spectroscopy
Nuclear magnetic resonance
Spectra
Spinning
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Summary:Solid-state super(13)C magic-angle spinning (MAS) NMR spectroscopy is used to investigate the structure of the Cu(ii)-based metal-organic frameworks (MOFs), HKUST-1 and STAM-1, and the structural changes occurring within these MOFs upon activation (dehydration). NMR spectroscopy is an attractive technique for the investigation of these materials, owing to its high sensitivity to local structure, without any requirement for longer-range order. However, interactions between nuclei and unpaired electrons in paramagnetic systems (e.g., Cu(ii)-based MOFs) pose a considerable challenge, not only for spectral acquisition, but also in the assignment and interpretation of the spectral resonances. Here, we exploit the rapid T sub(1) relaxation of these materials to obtain super(13)C NMR spectra using a spin-echo pulse sequence at natural abundance levels, and employ frequency-stepped acquisition to ensure uniform excitation of resonances over a wide frequency range. We then utilise selective super(13)C isotopic labelling of the organic linker molecules to enable an unambiguous assignment of NMR spectra of both MOFs for the first time. We show that the monomethylated linker can be recovered from STAM-1 intact, demonstrating not only the interesting use of this MOF as a protecting group, but also the ability (for both STAM-1 and HKUST-1) to recover isotopically-enriched linkers, thereby reducing significantly the overall cost of the approach.
ISSN:1463-9076
1463-9084
DOI:10.1039/c2cp43445h