Skip to content

Research at St Andrews

Investigation of zeolitic imidazolate frameworks using 13C and 15N solid-state NMR spectroscopy

Research output: Research - peer-reviewArticle

DOI

Open Access permissions

Open

Author(s)

Scott Sneddon, Juergen Kahr, Angelica F. Orsi, David J. Price, Daniel M. Dawson, Paul A. Wright, Sharon E. Ashbrook

School/Research organisations

Abstract

Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs) with extended three-dimensional networks of transition metal nodes (bridged by rigid imidazolate linkers), with potential applications in gas storage and separation, sensing and controlled delivery of drug molecules. Here, we investigate the use of 13C and 15N solid-state NMR spectroscopy to characterise the local structure and disorder in a variety of single- and dual-linker ZIFs. In most cases, a combination of a basic knowledge of chemical shifts typically observed in solution-state NMR spectroscopy and the use of dipolar dephasing NMR experiments to reveal information about quaternary carbon species are combined to enable spectral assignment. Accurate measurement of the anisotropic components of the chemical shift provided additional information to characterise the local environment and the possibility of trying to understand the relationships between NMR parameters and both local and long-range structure. First-principles calculations on some of the simpler, ordered ZIFs were possible, and provided support for the spectral assignments, while comparison of these model systems to more disordered ZIFs aided interpretation of the more complex spectra obtained. It is shown that 13C and 15N NMR are sufficiently sensitive to detect small changes in the local environment, e.g., functionalisation of the linker, crystallographic inequivalence and changes to the framework topology, while the relative proportion of each linker present can be obtained by comparing relative intensities of resonances corresponding to chemically-similar species in cross polarisation experiments with short contact times. Therefore, multinuclear NMR spectroscopy, and in particular the measurement of both isotropic and anisotropic parameters, offers a useful tool for the structural study of ordered and, in particular, disordered ZIFs.
Close

Details

Original languageEnglish
Pages (from-to)54-64
Number of pages11
JournalSolid State Nuclear Magnetic Resonance
Volume87
Early online date9 Sep 2017
DOIs
StatePublished - Oct 2017

    Research areas

  • Zeolitic imidazolate frameworks, Microporous materials, ZIFs, DFT, Solid-state NMR, 13C NMR, 15N NMR, CSA-amplified PASS

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

View graph of relations

Related by author

  1. Modulator-controlled synthesis of microporous STA-26, an interpenetrated 8,3-connected zirconium MOF with the the-i topology, and its reversible lattice shift

    Bumstead, A., Cordes, D. B., Dawson, D. M., Chakarova, K. K., Mihaylov, M. Y., Hobday, C. L., Düren, T., Hadjiivanov, K., Slawin, A. M. Z., Ashbrook, S. E., Prasad, R. R. R. & Wright, P. A. 23 Mar 2018 In : Chemistry - A European Journal. Early View, 13 p.

    Research output: Research - peer-reviewArticle

  2. A co-templating route to the synthesis of Cu SAPO STA-7, giving an active catalyst for the selective catalytic reduction of NO

    Picone, A. L., Warrender, S. J., Slawin, A. M. Z., Dawson, D. M., Ashbrook, S. E., Wright, P. A., Thompson, S. P., Gaberova, L., Llewellyn, P. L., Moulin, B., Vimont, A., Daturi, M., Park, M. B., Sung, S. K., Nam, I-S. & Hong, S. B. Dec 2011 In : Microporous and Mesoporous Materials. 146, 1-3, p. 36-47 12 p.

    Research output: Research - peer-reviewArticle

  3. Polymorphism, weak interactions and phase transitions in chalcogen-phosphorus heterocycles

    Sanz Camacho, P., Stanford, M., McKay, D., Dawson, D. M., Athukorala Arachchige, K. S., Cordes, D. B., Slawin, A. M. Z., Woollins, J. D. & Ashbrook, S. E. M. 22 May 2018 (Accepted/In press) In : Chemistry - A European Journal.

    Research output: Research - peer-reviewArticle

  4. 17O solid-state NMR spectroscopy of A2B2O7 oxides: quantitative isotopic enrichment and spectral acquisition?

    Fernandes, A., Moran, R., Sneddon, S., Dawson, D. M., McKay, D., Bignami, G. P. M., Blanc, F., Whittle, K. & Ashbrook, S. E. 14 Feb 2018 In : RSC Advances. 8, 13, p. 7089-7101

    Research output: Research - peer-reviewArticle

  5. 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: Research - peer-reviewArticle

Related by journal

  1. An NMR crystallographic approach to monitoring cation substitution in the aluminophosphate STA-2

    Seymour, V. R., Eschenroeder, E. C. V., Wright, P. A. & Ashbrook, S. E. M. 2014 In : Solid State Nuclear Magnetic Resonance. 11 p.

    Research output: Research - peer-reviewArticle

  2. Observation of "hidden" magnesium: First-principles calculations and 25Mg solid-state NMR of enstatite

    Griffin, J. M., Berry, A. J. & Ashbrook, S. E. M. Sep 2011 In : Solid State Nuclear Magnetic Resonance. 40, 2, p. 91-99 9 p.

    Research output: Research - peer-reviewArticle

  3. Fluorine-19 solid state NMR study of vinylidenefluoride polymers using selective relaxation filters

    Wormald, P., Ameduri, B., Harris, R. K. & Hazendonk, P. Sep 2006 In : Solid State Nuclear Magnetic Resonance. 30, p. 114-123 10 p.

    Research output: Research - peer-reviewArticle

ID: 251009391