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Issue 19, 2018
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On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids

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Abstract

The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs) via the measurement of the cross relaxation rate σ between two spins. In the intermolecular case, σ is proportional to rn, where r is the internuclear distance and n can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus σ can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for σ are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for 7Li–1H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.

Graphical abstract: On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids

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Publication details

The article was received on 08 Feb 2018, accepted on 25 Apr 2018 and first published on 25 Apr 2018


Article type: Paper
DOI: 10.1039/C8CP00911B
Citation: Phys. Chem. Chem. Phys., 2018,20, 13357-13364
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    On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids

    P. Martin, E. Salager, M. Forsyth, L. A. O’Dell and M. Deschamps, Phys. Chem. Chem. Phys., 2018, 20, 13357
    DOI: 10.1039/C8CP00911B

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