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

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Date
11/2012
Author
Dawson, Daniel M.
Jamieson, Lauren E.
Mohideen, M. Infas H.
McKinlay, Alistair C.
Smellie, Iain A.
Cadou, Romain
Keddie, Neil S.
Morris, Russell E.
Ashbrook, Sharon E.
Funder
EPSRC
EPSRC
EPSRC
EPSRC
EPSRC
EPSRC
Grant ID
EP/E041825/1
EP/F008384/1
EP/J501542/1
EP/J501542/1
EP/F018096/1
EP/J501542/1
Keywords
phosphates
Storage
Assignment
1st-principles calculations
CO2 adsorption
Crystal-structures
MAS NMR
Cross-polarization
Behavior
Complexes
QD Chemistry
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Abstract
Solid-state C-13 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-1 relaxation of these materials to obtain C-13 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 C-13 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.
Citation
Dawson , D M , Jamieson , L E , Mohideen , M I H , McKinlay , A C , Smellie , I A , Cadou , R , Keddie , N S , Morris , R E & Ashbrook , S E 2012 , ' High-resolution solid-state 13 C NMR spectroscopy of the paramagnetic metal-organic frameworks, STAM-1 and HKUST-1 ' , Physical Chemistry Chemical Physics , vol. 15 , no. 3 , pp. 919-929 . https://doi.org/10.1039/c2cp43445h
Publication
Physical Chemistry Chemical Physics
Status
Peer reviewed
DOI
https://doi.org/10.1039/c2cp43445h
ISSN
1463-9076
Type
Journal article
Rights
This is the author's version of this article. The published version © 2013 The Royal Society of Chemistry is available from http://pubs.rsc.org
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/4485

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