Skip to content

Research at St Andrews

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

Research output: Contribution to journalArticlepeer-review

DOI

Open Access permissions

Open

Author(s)

Daniel M. Dawson, Lauren E. Jamieson, M. Infas H. Mohideen, Alistair C. McKinlay, Iain A. Smellie, Romain Cadou, Neil S. Keddie, Russell E. Morris, Sharon E. Ashbrook

School/Research organisations

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.

Close

Details

Original languageEnglish
Pages (from-to)919-929
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume15
Issue number3
Early online date21 Nov 2012
DOIs
Publication statusPublished - Nov 2012

    Research areas

  • phosphates, Storage, Assignment, 1st-principles calculations, CO2 adsorption, Crystal-structures, MAS NMR, Cross-polarization, Behavior, Complexes

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Following the unusual breathing behaviour of 17O-enriched mixed-metal (Al,Ga)-MIL-53 using NMR crystallography

    Rice, C. M., Davis, Z. H., McKay, D., Bignami, G. P. M., Chitac, R. G., Dawson, D. M., Morris, R. E. & Ashbrook, S. E., 14 Jul 2020, In: Physical Chemistry Chemical Physics. 22, 26, p. 14514-14526 13 p.

    Research output: Contribution to journalArticlepeer-review

  2. 13C pNMR of “crumple zone” Cu(II) isophthalate metal-organic frameworks

    Dawson, D. M., Sansome, C. E. F., McHugh, L. N., McPherson, M. J., McCormick McPherson, L. J., Morris, R. E. & Ashbrook, S. E., 14 May 2019, In: Solid State Nuclear Magnetic Resonance. In press

    Research output: Contribution to journalArticlepeer-review

  3. Hydrolytic stability in hemilabile metal–organic frameworks

    McHugh, L. N., McPherson, M. J., McCormick, L. J., Morris, S. A., Wheatley, P. S., Teat, S. J., McKay, D., Dawson, D. M., Sansome, C. E. F., Ashbrook, S. E., Stone, C. A., Smith, M. W. & Morris, R. E., Nov 2018, In: Nature Chemistry. 10, 11, p. 1096–1102 7 p.

    Research output: Contribution to journalArticlepeer-review

  4. Cost-effective 17O enrichment and NMR spectroscopy of mixed-metal terephthalate metal-organic frameworks

    Bignami, G. P. M., Davis, Z. H., Dawson, D. M., Morris, S. A., Russell, S. E., McKay, D., Parke, R. E., Iuga, D., Morris, R. E. & Ashbrook, S. E., 28 Jan 2018, In: Chemical Science. 9, 4, p. 850-859

    Research output: Contribution to journalArticlepeer-review

  5. In situ solid-state NMR and XRD studies of the ADOR process and the unusual structure of zeolite IPC-6

    Morris, S. A., Bignami, G. P. M., Tian, Y., Navarro-Rojas, M., Firth, D. S., Cejka, J., Wheatley, P. S., Dawson, D. M., Slawinski, W. A., Wragg, D. S., Morris, R. E. & Ashbrook, S. E., Oct 2017, In: Nature Chemistry. 9, 10, p. 1012-1018 7 p.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. Physical Chemistry Chemical Physics (Journal)

    Finlay Morrison (Reviewer)

    2009 → …

    Activity: Publication peer-review and editorial work typesPeer review of manuscripts

Related by journal

  1. A general model to optimise CuII labelling efficiency of double-histidine motifs for pulse dipolar EPR applications

    Wort, J., Ackermann, K., Norman, D. & Bode, B. E., 14 Feb 2021, In: Physical Chemistry Chemical Physics. 23, 6, p. 3810-3819 10 p.

    Research output: Contribution to journalArticlepeer-review

  2. A quinone based single-molecule switch as building block for molecular electronics

    Früchtl, H. A. & van Mourik, T., 21 Jan 2021, In: Physical Chemistry Chemical Physics. 23, 3, p. 1811-1814

    Research output: Contribution to journalArticlepeer-review

  3. The contribution of non-classical CHax∙∙∙OC hydrogen bonds to the anomeric effect in fluoro and oxa-methoxycyclohexanes

    Piscelli, B., O'Hagan, D. & Cormanich, R., 2 Mar 2021, In: Physical Chemistry Chemical Physics. 23, 10, p. 5845-5851

    Research output: Contribution to journalArticlepeer-review

  4. Effects of crystal size on methanol to hydrocarbon conversion over single crystals of ZSM-5 studied by synchrotron infrared microspectroscopy

    Minova, I. B., Matam, S. K., Greenaway, A., Catlow, C. R. A., Frogley, M. D., Cinque, G., Wright, P. A. & Howe, R. F., 14 Sep 2020, In: Physical chemistry chemical physics : PCCP. 22, 34, p. 18849-18859 11 p.

    Research output: Contribution to journalArticlepeer-review

  5. Following the unusual breathing behaviour of 17O-enriched mixed-metal (Al,Ga)-MIL-53 using NMR crystallography

    Rice, C. M., Davis, Z. H., McKay, D., Bignami, G. P. M., Chitac, R. G., Dawson, D. M., Morris, R. E. & Ashbrook, S. E., 14 Jul 2020, In: Physical Chemistry Chemical Physics. 22, 26, p. 14514-14526 13 p.

    Research output: Contribution to journalArticlepeer-review

ID: 46702547

Top