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Title: Preparation and investigation into the optical properties of air sensitive f-block complexes
Author: Randall, Simon
ISNI:       0000 0004 6497 6571
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2015
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The aim of this project is to prepare novel uranium complexes in coordination environments suited to the analysis of their photoluminescence properties with a view to the expansion of this technique in actinide chemistry. Chapter One outlines the chemistry of uranium with some highlights on the reactivity it possesses for the less stable oxidation states. Following on from this is a précis of the limited photoluminescence data available for uranium in non-aqueous environments and potential avenues of improvement. Chapter Two details the preparation and characterisation of lanthanide partially oligomerised silsesquioxane complexes in anhydrous conditions and their single photon optical properties, with a preliminary examination of the ability of these ligands to support an upconverting lanthanide centre with observations of the first solution phase upconverting erbium complex. Chapter Three expands on these ligands by applying them to uranium and examining the behaviour of uranium in the presence of these analogues to natural silica and the unusual redox behaviour this has supported, with the observation of trivalent, tetravalent, pentavalent and hexavalent species of uranium. Chapter Four re-examines the previously characterised but largely abandoned pentahalogenooxouranium anion UOCl5- with an examination of the optical properties and initial studies into the proclivity of this species to undergo disproportionation reactions with evidence suggesting an oxygen transfer mechanism. Chapter Five details attempts to prepare pentavalent uranyl complexes of the hexamethyldisilylamide ligand, including a diamond core system with relevance to the investigation of the disproportionation mechanism, and explores the emission spectroscopy of isolated pentavalent uranyl species for the first time. Chapter Six records the experimental details and characterising data for the reactions discussed in this work.
Supervisor: Natrajan, Louise Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available