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13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks

13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks
13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks

NMR spectroscopy of paramagnetic materials (pNMR) has the potential to provide great structural insight, but many challenges remain in interpreting the spectra in detail. This work presents a study of a series of structurally analogous metal-organic frameworks (MOFs) based on 5-substituted isophthalate linkers and Cu(II) paddlewheel dimers, of interest owing to their “crumple zone” structural rearrangement on dehydration/rehydration. 13C MAS NMR spectra reveal a wide variation in the observed resonance position for chemically similar C species in the different MOFs but, despite this, resonances are overlapped in several cases. However, by considering a combination of the integration of quantitative spectra, the resonance position as a function of temperature and T1 relaxation measurements, the spectra can be fully assigned. It is also demonstrated that the prototypical MOF in this series, STAM-1, displays a crumple zone rearrangement on dehydration, similar to the well-characterised 5-ethoxyisophthalate MOF (STAM-17-OEt) although, while the materials have similar local C environments, dehydrated STAM-1 exhibits less long-range order.

C, Cu(II), Fast magic angle spinning, Metal-organic frameworks, Paddlewheel dimer, Paramagnetic NMR
0926-2040
44-50
Dawson, Daniel M.
b73d9ebe-ecf6-49ad-a205-a57bb9ed1e8c
Sansome, Charlotte E.F.
91028b1c-53c0-4a69-a24d-da37c61499b3
McHugh, Lauren N.
cf4f6505-763b-478a-9170-6057e648f454
McPherson, Matthew J.
d3c78165-4cd3-4607-bdb4-465ce844bc96
McCormick McPherson, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Morris, Russell E.
0c724305-d30c-4be8-8b1f-bec10ca5f91c
Ashbrook, Sharon E.
7f280ee4-6793-4956-aeb7-e933c8fafb1d
Dawson, Daniel M.
b73d9ebe-ecf6-49ad-a205-a57bb9ed1e8c
Sansome, Charlotte E.F.
91028b1c-53c0-4a69-a24d-da37c61499b3
McHugh, Lauren N.
cf4f6505-763b-478a-9170-6057e648f454
McPherson, Matthew J.
d3c78165-4cd3-4607-bdb4-465ce844bc96
McCormick McPherson, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Morris, Russell E.
0c724305-d30c-4be8-8b1f-bec10ca5f91c
Ashbrook, Sharon E.
7f280ee4-6793-4956-aeb7-e933c8fafb1d

Dawson, Daniel M., Sansome, Charlotte E.F., McHugh, Lauren N., McPherson, Matthew J., McCormick McPherson, Laura J., Morris, Russell E. and Ashbrook, Sharon E. (2019) 13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks. Solid State Nuclear Magnetic Resonance, 101, 44-50. (doi:10.1016/j.ssnmr.2019.05.005).

Record type: Article

Abstract

NMR spectroscopy of paramagnetic materials (pNMR) has the potential to provide great structural insight, but many challenges remain in interpreting the spectra in detail. This work presents a study of a series of structurally analogous metal-organic frameworks (MOFs) based on 5-substituted isophthalate linkers and Cu(II) paddlewheel dimers, of interest owing to their “crumple zone” structural rearrangement on dehydration/rehydration. 13C MAS NMR spectra reveal a wide variation in the observed resonance position for chemically similar C species in the different MOFs but, despite this, resonances are overlapped in several cases. However, by considering a combination of the integration of quantitative spectra, the resonance position as a function of temperature and T1 relaxation measurements, the spectra can be fully assigned. It is also demonstrated that the prototypical MOF in this series, STAM-1, displays a crumple zone rearrangement on dehydration, similar to the well-characterised 5-ethoxyisophthalate MOF (STAM-17-OEt) although, while the materials have similar local C environments, dehydrated STAM-1 exhibits less long-range order.

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More information

Accepted/In Press date: 10 May 2019
e-pub ahead of print date: 14 May 2019
Published date: 1 September 2019
Keywords: C, Cu(II), Fast magic angle spinning, Metal-organic frameworks, Paddlewheel dimer, Paramagnetic NMR

Identifiers

Local EPrints ID: 438505
URI: http://eprints.soton.ac.uk/id/eprint/438505
ISSN: 0926-2040
PURE UUID: 2f4105b7-72df-4761-abb7-bc0a64e086a9
ORCID for Laura J. McCormick McPherson: ORCID iD orcid.org/0000-0002-6634-4717

Catalogue record

Date deposited: 11 Mar 2020 17:33
Last modified: 26 Nov 2021 03:21

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Contributors

Author: Daniel M. Dawson
Author: Charlotte E.F. Sansome
Author: Lauren N. McHugh
Author: Matthew J. McPherson
Author: Russell E. Morris
Author: Sharon E. Ashbrook

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