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Issue 20, 2019
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Determination of element–deuterium bond lengths in Zintl phase deuterides by 2H-NMR

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Abstract

The Zintl phase deuterides CaSiD4/3, SrSiD5/3, BaSiD2, SrGeD4/3, BaGeD5/3 and BaSnD4/3 were investigated by nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to reliably determine element–deuterium bond lengths. These compounds show deuterium bound to the polyanion and deuteride ions in tetrahedral cationic voids. With 2H-NMR experiments we characterised the individual signals of the two distinct crystal sites. Quadrupolar coupling constants (CQ) of the anion-binding site were determined as 58 to 78 kHz (Si compounds), 51 to 61 kHz (Ge compounds) and 38 kHz (Sn compound). These values agree well with the quadrupole couplings derived from DFT using optimized structural models. We further calculated the general element–deuterium distance dependency of CQ using DFT methods that allow an accurate determination of bond lengths via the 2H quadrupole interaction. The thus determined bond lengths are evaluated as d(Si–D) = 1.53–1.59 Å, d(Ge–D) = 1.61–1.65 Å and d(Sn–D) = 1.86 Å. Chemical shifts of the anion-binding site range from 0.3 to 1.3 ppm. The isotropic chemical shifts of the tetrahedral sites are 5.1 ppm (CaSiD4/3), 7.0 to 10.0 ppm (Sr compounds) and 10.7 to 11.6 ppm (Ba compounds).

Graphical abstract: Determination of element–deuterium bond lengths in Zintl phase deuterides by 2H-NMR

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Publication details

The article was received on 16 Jan 2019, accepted on 03 May 2019 and first published on 03 May 2019


Article type: Paper
DOI: 10.1039/C9CP00292H
Phys. Chem. Chem. Phys., 2019,21, 10594-10602
  • Open access: Creative Commons BY-NC license
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    Determination of element–deuterium bond lengths in Zintl phase deuterides by 2H-NMR

    R. Guehne, H. Auer, H. Kohlmann, J. Haase and M. Bertmer, Phys. Chem. Chem. Phys., 2019, 21, 10594
    DOI: 10.1039/C9CP00292H

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