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

Daniel M. Dawson; Charlotte E. F. Sansome; Lauren N. McHugh; Matthew J. McPherson; Laura J. McCormick McPherson; Russell E. Morris; Sharon E. Ashbrook

doi:10.1016/j.ssnmr.2019.05.005

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

Daniel M. Dawson, Charlotte E. F. Sansome, Lauren N. McHugh, Matthew J. McPherson, Laura J. McCormick McPherson, Russell E. Morris, Sharon E. Ashbrook

Research output: Contribution to journal › Article › peer-review

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 of the MOFs 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 similar crumple zone rearrangement on dehydration 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.

Original language	English
Journal	Solid State Nuclear Magnetic Resonance
Volume	In press
Early online date	14 May 2019
DOIs	https://doi.org/10.1016/j.ssnmr.2019.05.005
Publication status	E-pub ahead of print - 14 May 2019

Keywords

Paramagnetic NMR
Metal-organic frameworks
13C
Fast magic angle spinning
Cu(II)
Paddlewheel dimer

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10.1016/j.ssnmr.2019.05.005

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Copyright © 2019 Elsevier Inc. All rights reserved. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1016/j.ssnmr.2019.05.005
Accepted author manuscript, 845 KBLicence: CC BY-NC-ND
ESI_finalAccepted author manuscript, 330 KB

RS Wolfson Merit Award: Exploiting NMR spectroscopy: Local structure and disorder in solids
Ashbrook, S. E. (PI)
The Royal Society
1/09/15 → 31/08/20
Project: Standard

13C pNMR of “Crumple Zone” Cu(II) Isophthalate Metal-Organic Frameworks (dataset)
Dawson, D. M. (Creator), Sansome, C. E. F. (Creator), McHugh, L. N. (Creator), McPherson, M. J. (Creator), McCormick, L. J. (Creator), Morris, R. E. (Creator) & Ashbrook, S. E. M. (Creator), University of St Andrews, 17 May 2019
DOI: 10.17630/0c27a0c9-aa47-47e4-b30a-a215976c3dbe
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Cite this

@article{d9b91cc80f9649468d099448f1c266ef,

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

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 of the MOFs 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 similar crumple zone rearrangement on dehydration 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.",

keywords = "Paramagnetic NMR, Metal-organic frameworks, 13C, Fast magic angle spinning, Cu(II), Paddlewheel dimer",

author = "Dawson, {Daniel M.} and Sansome, {Charlotte E. F.} and McHugh, {Lauren N.} and McPherson, {Matthew J.} and {McCormick McPherson}, {Laura J.} and Morris, {Russell E.} and Ashbrook, {Sharon E.}",

note = "SEA thanks the Royal Society and Wolfson Foundation for a merit award. REM and LNM thank the EPSRC for support (EP/N50936X/1).",

year = "2019",

month = may,

day = "14",

doi = "10.1016/j.ssnmr.2019.05.005",

language = "English",

volume = "In press",

journal = "Solid State Nuclear Magnetic Resonance",

issn = "0926-2040",

publisher = "Elsevier",

}

TY - JOUR

T1 - 13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks

AU - Dawson, Daniel M.

AU - Sansome, Charlotte E. F.

AU - McHugh, Lauren N.

AU - McPherson, Matthew J.

AU - McCormick McPherson, Laura J.

AU - Morris, Russell E.

AU - Ashbrook, Sharon E.

N1 - SEA thanks the Royal Society and Wolfson Foundation for a merit award. REM and LNM thank the EPSRC for support (EP/N50936X/1).

PY - 2019/5/14

Y1 - 2019/5/14

N2 - 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 of the MOFs 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 similar crumple zone rearrangement on dehydration 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.

AB - 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 of the MOFs 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 similar crumple zone rearrangement on dehydration 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.

KW - Paramagnetic NMR

KW - Metal-organic frameworks

KW - 13C

KW - Fast magic angle spinning

KW - Cu(II)

KW - Paddlewheel dimer

U2 - 10.1016/j.ssnmr.2019.05.005

DO - 10.1016/j.ssnmr.2019.05.005

M3 - Article

SN - 0926-2040

VL - In press

JO - Solid State Nuclear Magnetic Resonance

JF - Solid State Nuclear Magnetic Resonance

ER -

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

Abstract

Keywords

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Projects

RS Wolfson Merit Award: Exploiting NMR spectroscopy: Local structure and disorder in solids

Datasets

13C pNMR of “Crumple Zone” Cu(II) Isophthalate Metal-Organic Frameworks (dataset)

Cite this

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