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Title: From linear to cyclic anion receptors : high affinity receptors and sensors for oxo-anions
Author: Brooks, Simon James
ISNI:       0000 0001 3482 3476
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 2006
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This thesis reports the synthesis and study of the coordination properties of a variety of novel organic anion receptors. A series of receptors based upon 1,2-phenylenediamine with varying hydrogen-bonding geometries have been investigated. Of these it has been observed that compounds that are based upon bis-urea functionality serve as excellent receptors for oxo-anions, in particular carboxylate anions, in DMSO solutions. A macrocyclic amido-urea derivative and various acyclic fragments of the structure have been synthesized and their anion binding properties determined. It has been found that the macrocycle displays significantly enhanced anion binding properties, in comparison to its fragments, with the especially high binding observed with carboxylates. Analysis of the binding data reveals that the macrocycle binds anions through differing binding modes depending upon anion size and shape. Five 1,3-dicarboxamidoanthraquinone-based receptors have been synthesized and their anion binding properties investigated. In solution the receptors display moderate determinable selectivity for dihydrogen phosphate over the other oxo-anions, although fluoride interacts strongly the data could not be fitted to a binding model. The electrochemistry of the anthraquinone system has been investigated in both the presence and absence of fluoride and it has been determined that stabilizing interactions to the oxygen atoms from the amide groups may be overcome upon addition of fluoride anions, allowing electrochemical sensing of the fluoride species. Various anthracene-based receptors have been synthesized in order to investigate differing hydrogen-bonding motifs. Two alternative amide motifs have been demonstrated to offer selectivities consistent with their respective hydrogen bonding arrays. A further examination of bis-urea based anthracene receptors reveal selectivity for carboxylates, with fluorescence quenching observed upon addition of coordinating anions.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available