| DOI | Resolve DOI: https://doi.org/10.1134/S0022476616020104 |
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| Author | Search for: Terskikh, V. V.; Search for: Pawsey, S.; Search for: Ripmeester, J. A.1 |
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| Affiliation | - National Research Council of Canada. Security and Disruptive Technologies
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| Format | Text, Article |
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| Subject | ³⁵Cl NMR; ³⁵Cl NQR; Selenium; Tellurium; Hexachloride; DFT calculations; CASTEP NMR |
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| Abstract | We report solid-state ³⁵Cl NMR spectra in three hexachlorides, (NH₄)₂SeCl₆, (NH₄)₂TeCl₆ and Rb₂TeCl₆. The C Q (³⁵Cl) quadrupole coupling constants in the three compounds were found to be 41.4±0.1 MHz, 30.3±0.1 MHz and 30.3±0.1 MHz, respectively, some of the largest C Q (³⁵Cl) quadrupole coupling constants ever measured in polycrystalline powdered solids directly via ³⁵Cl NMR spectroscopy. The ³⁵Cl EFG tensors are axial in all three cases reflecting the C ₄ᵥ point group symmetry of the chlorine sites. ³⁵Cl NMR experiments in these compounds were only made possible by employing the WURST-QCPMG pulse sequence in the ultrahigh magnetic field of 21.1 T. ³⁵Cl NMR results agree with the earlier reported ³⁵Cl NQR values and with the complementary plane-wave DFT calculations. The origin of the very large C Q (³⁵Cl) quadrupole coupling constants in these and other main-group chlorides lies in the covalent-type chlorine bonding. The ionic bonding in the ionic chlorides results in significantly reduced C Q (³⁵Cl) values as illustrated with triphenyltellurium chloride Ph₃TeCl. The high sensitivity of ³⁵Cl NMR to the chlorine coordination environment is demonstrated using tetrachlorohydroxotellurate hydrate K[TeCl₄(OH)]∙0.5H₂O as an example. ¹²⁵Te MAS NMR experiments were performed for tellurium compounds to support ³⁵Cl NMR findings. |
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| Publication date | 2016-03 |
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| Publisher | Springer International Publishing |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| Identifier | 368 |
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| NPARC number | 23000403 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | ced94e84-cc64-46a6-a416-dacc2056e741 |
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| Record created | 2016-07-13 |
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| Record modified | 2020-03-16 |
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