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Title: New redox active ion sensors : synthetic, electrochemical, spectroscopic and guest binding studies
Author: Hartigan, Hilary Jean Noelle
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2002
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The preparation of two new [18]aneS4N2 macrocycles with conjugated links to redox-active Co centres has been achieved [(CpCo)2S4N2 and (CpCo)S4N2 via reaction of an [18aneS4N2 bisthione macrocycle with CpCoLL, LL = COD or (CO)2. Optimisation of this reaction had lead to a high yielding and selective route to the ligand containing one Co centre. The characterisation of these complexes is described in detail and includes a study of the spectro-electrochemical, electrochemical, EPR and UV/Vis spectroscopic data. The second section of this thesis concentrates on complexation studies of these redox-active cobalt macrocycles with a variety of transition metal ions. The metal ions are a mixture of late transition metal and heavy metal ions and include possible pollutant species present within aqueous environmental systems. They include, AgI, FeII, CoII, NiII, CuI, CuII, PbII, CdII, HgII, and SnII. The studies was carried out in variety of solvent systems and complexations were followed by modifications in electrochemical behaviour and UV/Vis spectroscopy. Strong interactions were observed between the Co centre and the guest metal ion in the macrocycle in several cases and encouraging results are reported indicating the use of these systems in Ion Sensing. In particular the complexation study carried out with AgI and NiII proved to be the most significant. A route to the method of complexation of the ions, AgI, FeII, CoII, NiII, CuI, and CuII is proposed with a suggestion for an alternative pathway for the complexation of the heavier metals, SnII, PbII, HgII and CdII is also given.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available