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An investigation into the molecular recognition and sensing of anions, especially of alkylcarbamates and related species

An investigation into the molecular recognition and sensing of anions, especially of alkylcarbamates and related species
An investigation into the molecular recognition and sensing of anions, especially of alkylcarbamates and related species
This thesis reports the synthesis and study of the anion recognition properties of a variety of synthetic organic and inorganic receptors. A series of known anion receptors containing a common urea and varying alkyl and aryl substituents have been investigated for their ability to bind the alkylcarbamate portion of two alkylammonium-alkylcarbamate salts and the CO2 adduct of a cyclic amidine, in an investigation into novel CO2 fixation strategies. Chemical shift changes were used to observe relative binding strengths for interactions between the alkylcarbamate and the receptors in DMSO-d6. The results show that it is possible to bind the alkylcarbamate anion in the presence of the primary alkylammonium cation, when a receptor of sufficient strength is employed. The strength of this interaction was increased when 18-crown-6 was added, which acts as a receptor for the alkylammonium cation. The CO2 adduct of the cyclic amidine, (1,4,5,6, tetrahydropyrimidine) was shown to have the strongest interactions with the receptor series. Several Schiff-base and urea containing receptors have been synthesised and assessed for anion complexation properties in solution using 1H NMR in DMSO-d6 : water mixtures. These are selective for acetate, benzoate and dihydrogen phosphate over chloride and hydrogen sulfate, and exhibit a mixture of 1:1 and 2:1, (guest:host), binding stoichiometries in several cases. Zinc(II) and cobalt(II) chloride complexes of one of this series were synthesised. The cobalt(II)chloride complex was observed to be a stark colorimetric indicator for chloride and dihydrogen phosphate. A number of isophthalamide derivatives containing activated NH and / or CH protons have been synthesised and assessed for anion complexation solution using 1H NMR in DMSOd6. Their interactions with fluoride, chloride and bromide were investigated, which demonstrate a significant contribution from the activated CH protons
Edwards, Peter R.
aaa0f75a-0fd5-490a-ba73-a420189e4695
Edwards, Peter R.
aaa0f75a-0fd5-490a-ba73-a420189e4695
Grossel, Martin
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Edwards, Peter R. (2010) An investigation into the molecular recognition and sensing of anions, especially of alkylcarbamates and related species. University of Southampton, School of Chemistry, Doctoral Thesis, 234pp.

Record type: Thesis (Doctoral)

Abstract

This thesis reports the synthesis and study of the anion recognition properties of a variety of synthetic organic and inorganic receptors. A series of known anion receptors containing a common urea and varying alkyl and aryl substituents have been investigated for their ability to bind the alkylcarbamate portion of two alkylammonium-alkylcarbamate salts and the CO2 adduct of a cyclic amidine, in an investigation into novel CO2 fixation strategies. Chemical shift changes were used to observe relative binding strengths for interactions between the alkylcarbamate and the receptors in DMSO-d6. The results show that it is possible to bind the alkylcarbamate anion in the presence of the primary alkylammonium cation, when a receptor of sufficient strength is employed. The strength of this interaction was increased when 18-crown-6 was added, which acts as a receptor for the alkylammonium cation. The CO2 adduct of the cyclic amidine, (1,4,5,6, tetrahydropyrimidine) was shown to have the strongest interactions with the receptor series. Several Schiff-base and urea containing receptors have been synthesised and assessed for anion complexation properties in solution using 1H NMR in DMSO-d6 : water mixtures. These are selective for acetate, benzoate and dihydrogen phosphate over chloride and hydrogen sulfate, and exhibit a mixture of 1:1 and 2:1, (guest:host), binding stoichiometries in several cases. Zinc(II) and cobalt(II) chloride complexes of one of this series were synthesised. The cobalt(II)chloride complex was observed to be a stark colorimetric indicator for chloride and dihydrogen phosphate. A number of isophthalamide derivatives containing activated NH and / or CH protons have been synthesised and assessed for anion complexation solution using 1H NMR in DMSOd6. Their interactions with fluoride, chloride and bromide were investigated, which demonstrate a significant contribution from the activated CH protons

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Published date: 22 June 2010
Organisations: University of Southampton

Identifiers

Local EPrints ID: 173961
URI: https://eprints.soton.ac.uk/id/eprint/173961
PURE UUID: c84dde87-c182-4e1a-863e-76a63d8907c3
ORCID for Martin Grossel: ORCID iD orcid.org/0000-0001-7469-6854

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Date deposited: 19 May 2011 12:50
Last modified: 06 Jun 2018 13:09

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