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A solid-state 35/37Cl NMR study of a chloride ion receptor and a GIPAW-DFT study of chlorine NMR interaction tensors in organic hydrochlorides

Chapman, R. P., Hiscock, Jennifer R., Gale, Philip A., Bryce, D. L. (2011) A solid-state 35/37Cl NMR study of a chloride ion receptor and a GIPAW-DFT study of chlorine NMR interaction tensors in organic hydrochlorides. Canadian Journal of Chemistry, 89 (7). pp. 822-834. ISSN 0008-4042. (doi:10.1139/v10-177) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:70822)

The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided. (Contact us about this Publication)
Official URL
https://doi.org/10.1139/v10-177

Abstract

The results of a 35/37Cl solid-state nuclear magnetic resonance (SSNMR) study of the 1-butyl-3-methylimidazolium chloride complex of meso-octamethylcalix[4]pyrrole (1) are reported. Line shapes obtained from magic-angle-spinning and stationary powder samples collected at 9.4 and 21.1 T are analyzed to provide the 35/37Cl quadrupolar tensor and chemical shift (CS) tensor and their relative orientation. The relatively high symmetry of the chloride ion coordination environment is manifested in the small value of the quadrupole coupling constant, CQ(35Cl) = 1.0 MHz. The isotropic chemical shift of 120 ppm (with respect to NaCl(s)) is at the upper edge of the typical range seen for organic hydrochlorides. Consideration of chemical shift anisotropy (span, ? = 50 ppm) and non-coincidence of the quadrupolar and CS tensors were essential to properly simulate the experimental spectra. The utility of gauge-including projector-augmented wave density functional theory (GIPAW-DFT) calculations of chlorine quadrupolar and CS tensors in organic chlorides was explored by validation against available benchmark experimental data for solid amino acid hydrochlorides. The calculations are shown to systematically overestimate the value of the 35Cl quadrupole coupling constant. Additional calculations on various hydrated and solvated models of 1 are consistent with a structure in which solvent and water of hydration are absent.

Item Type: Article
DOI/Identification number: 10.1139/v10-177
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences
Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Jennifer Hiscock
Date Deposited: 07 Dec 2018 16:22 UTC
Last Modified: 23 Jan 2020 04:15 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/70822 (The current URI for this page, for reference purposes)
Hiscock, Jennifer R.: https://orcid.org/0000-0002-1406-8802
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