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An investigation into the molecular recognition, structural and extraction properties of hydrogen bonding anion receptors

An investigation into the molecular recognition, structural and extraction properties of hydrogen bonding anion receptors
An investigation into the molecular recognition, structural and extraction properties of hydrogen bonding anion receptors

This thesis reports the synthesis and study of the molecular recognition properties of a variety of synthetic organic receptors. An investigation into the ion-pair recognition properties of calix[4]pyrrole derivatives has been carried' out with a number of organic salts. Crystallographic studies revealed that the anion induced cavity of the calix[4]pyrrole derivatives were able to accommodate cationic species within it. Proton NMR titrations were performed with me50-octacalix[4]pyrrole and a variety of organic chloride and bromide salts in dichloromethane-d2- The results show that the chloride and bromide stability constants increase with a change of cation (tetrabutylammonium < imidazolium < pyridinium). This effect was not observed in DMSO-d6/0.5% water solution. Two cleft-like bis-indole anion receptors have been synthesised and their anion binding studies showed a high selectivity for fluoride in DMSO-water solutions. X-ray crystallography showed that the receptors cavity is able to encapsulate the fluoride anion whereas the larger chloride anion is too large and perches above the plane of the cavity. A series of 2,7- functionalized indoles have been synthesized with appended amide and/or urea or thiourea groups. Anion complexation studies show a marked difference in the mode of interaction of carboxylates with indole-ureas vs indole-amides. A number of simple receptors have been synthesised and investigated as potential sulfuric acid extraction ligands for the hydrometallurgical extraction of nickel(II) sulfate by a dual-host system. Liquid-liquid solvent extraction experiments showed that the dual-host systems containing an isophthalamide based ligand extracted ~90% of nickel(II) sulfate at pH 4.9 which corresponds well to pH values likely in nickel extraction circuits.

University of Southampton
Bates, Gareth Williams
Bates, Gareth Williams

Bates, Gareth Williams (2008) An investigation into the molecular recognition, structural and extraction properties of hydrogen bonding anion receptors. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

This thesis reports the synthesis and study of the molecular recognition properties of a variety of synthetic organic receptors. An investigation into the ion-pair recognition properties of calix[4]pyrrole derivatives has been carried' out with a number of organic salts. Crystallographic studies revealed that the anion induced cavity of the calix[4]pyrrole derivatives were able to accommodate cationic species within it. Proton NMR titrations were performed with me50-octacalix[4]pyrrole and a variety of organic chloride and bromide salts in dichloromethane-d2- The results show that the chloride and bromide stability constants increase with a change of cation (tetrabutylammonium < imidazolium < pyridinium). This effect was not observed in DMSO-d6/0.5% water solution. Two cleft-like bis-indole anion receptors have been synthesised and their anion binding studies showed a high selectivity for fluoride in DMSO-water solutions. X-ray crystallography showed that the receptors cavity is able to encapsulate the fluoride anion whereas the larger chloride anion is too large and perches above the plane of the cavity. A series of 2,7- functionalized indoles have been synthesized with appended amide and/or urea or thiourea groups. Anion complexation studies show a marked difference in the mode of interaction of carboxylates with indole-ureas vs indole-amides. A number of simple receptors have been synthesised and investigated as potential sulfuric acid extraction ligands for the hydrometallurgical extraction of nickel(II) sulfate by a dual-host system. Liquid-liquid solvent extraction experiments showed that the dual-host systems containing an isophthalamide based ligand extracted ~90% of nickel(II) sulfate at pH 4.9 which corresponds well to pH values likely in nickel extraction circuits.

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Published date: 2008

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Local EPrints ID: 466446
URI: http://eprints.soton.ac.uk/id/eprint/466446
PURE UUID: c47f27d7-233f-4eca-94f1-8deb8e81753a

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Date deposited: 05 Jul 2022 05:16
Last modified: 05 Jul 2022 07:34

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Author: Gareth Williams Bates

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