NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study

Zhipeng Ke; Lauren Jamieson; Daniel M. Dawson; Sharon E.  Ashbrook; Michael Buehl

doi:10.1016/j.ssnmr.2019.04.004

NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study

Zhipeng Ke, Lauren Jamieson, Daniel M. Dawson, Sharon E. Ashbrook, Michael Buehl

Research output: Contribution to journal › Special issue › peer-review

Abstract

We report solid-state ¹³C NMR spectra of urea-loaded copper benzoate, Cu₂(C₆H₅CO₂)₄^.2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ(¹³C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed ¹³C chemical shifts is below 30 ppm over a range of more than 1100 ppm.

Original language	English
Journal	Solid State Nuclear Magnetic Resonance
Volume	In press
Early online date	20 Apr 2019
DOIs	https://doi.org/10.1016/j.ssnmr.2019.04.004
Publication status	E-pub ahead of print - 20 Apr 2019

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pubZhipeng-ssNMR
Copyright © 2019 Published by Elsevier Inc. 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.2019.04.004
Accepted author manuscript, 564 KBLicence: CC BY-NC-ND

NMR Crystallography: Collaborative Computational Project in NMR Crystallography - Collaborative Agreement
Ashbrook, S. E. (PI)
EPSRC
1/04/15 → 31/03/20
Project: Standard

NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study (dataset)
Ke, Z. (Creator), Jamieson, L. (Creator), Dawson, D. M. (Creator), Ashbrook, S. E. M. (Creator) & Buehl, M. (Creator), University of St Andrews, 29 May 2019
DOI: 10.17630/15c0e2d2-4fe0-4033-bd6d-a674db24f06f
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@article{e914448201024a0799eada8bba07b920,

title = "NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study",

abstract = "We report solid-state 13C NMR spectra of urea-loaded copper benzoate, Cu2(C6H5CO2)4.2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ(13C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed 13C chemical shifts is below 30 ppm over a range of more than 1100 ppm.",

author = "Zhipeng Ke and Lauren Jamieson and Dawson, {Daniel M.} and Ashbrook, {Sharon E.} and Michael Buehl",

note = "We thank EaStCHEM and the School of Chemistry for support. Computations were carried out on a local Opteron PC cluster maintained by Dr. H. Fr{\"u}chtl. This work was supported by the EPSRC through the Collaborative Computational Project on NMR Crystallography (CCP-NC), via EP/M022501/1. SEA would also like to thank the Royal Society and Wolfson Foundation for a merit award. ZK gratefully appreciates a scholarship from the China Scholarship Council (CSC). ",

year = "2019",

month = apr,

day = "20",

doi = "10.1016/j.ssnmr.2019.04.004",

language = "English",

volume = "In press",

journal = "Solid State Nuclear Magnetic Resonance",

issn = "0926-2040",

publisher = "Elsevier",

}

TY - JOUR

T1 - NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study

AU - Ke, Zhipeng

AU - Jamieson, Lauren

AU - Dawson, Daniel M.

AU - Ashbrook, Sharon E.

AU - Buehl, Michael

N1 - We thank EaStCHEM and the School of Chemistry for support. Computations were carried out on a local Opteron PC cluster maintained by Dr. H. Früchtl. This work was supported by the EPSRC through the Collaborative Computational Project on NMR Crystallography (CCP-NC), via EP/M022501/1. SEA would also like to thank the Royal Society and Wolfson Foundation for a merit award. ZK gratefully appreciates a scholarship from the China Scholarship Council (CSC).

PY - 2019/4/20

Y1 - 2019/4/20

N2 - We report solid-state 13C NMR spectra of urea-loaded copper benzoate, Cu2(C6H5CO2)4.2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ(13C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed 13C chemical shifts is below 30 ppm over a range of more than 1100 ppm.

AB - We report solid-state 13C NMR spectra of urea-loaded copper benzoate, Cu2(C6H5CO2)4.2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ(13C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed 13C chemical shifts is below 30 ppm over a range of more than 1100 ppm.

U2 - 10.1016/j.ssnmr.2019.04.004

DO - 10.1016/j.ssnmr.2019.04.004

M3 - Special issue

SN - 0926-2040

VL - In press

JO - Solid State Nuclear Magnetic Resonance

JF - Solid State Nuclear Magnetic Resonance

ER -

NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study

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NMR Crystallography: Collaborative Computational Project in NMR Crystallography - Collaborative Agreement

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NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study (dataset)

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