Exploring Photochemical and Redox Reactivity of Four-Coordinated Organoboron Compounds
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Authors
Li, Cally
Date
Type
thesis
Language
eng
Keyword
Photochemistry , Organoboron , Electrochemistry
Alternative Title
Abstract
The works described herein are broadly concerned with exploring the characteristic reactivities and properties of four-coordinated organoboron systems, to fully understand and cultivate their utility and applicability. In particular, two different classes of chelate boron compounds are studied, namely N,C- and N,O-, with emphasis on investigating their response to external stimuli and unveiling the unique photophysical/optical properties inherent to these systems.
The first section of work described in this thesis focuses on the synthesis and study of new unsymmetrical N,C-chelate organoboron systems bearing two different aryl groups at the boron centre. These phenylpyrazolyl-chelated compounds have been found to undergo a rare, two-stage regioselective photoisomerization. The initial transformation is a di-π-borate rearrangement that affords yellow azaboratabisnorcaradiene isomers which are subsequently converted to unprecedented 14aH- diazaborepins. Spectroscopic and computational studies provide insight into the formation and properties of these unique systems.
A new series of N,O-chelate methylaminoanthraquinone-bridged diboron complexes have also been synthesized and their redox behaviour studied via cyclic voltammetry, EPR, and UV/Vis-NIR spectroelectrochemistry. It was found that coordination of boron to a commercial dye offered a redox- stabilizing effect, as well as tuning of the compounds’ colors and electron-accepting/-donating ability based on the substituents attached to boron. BF2 chelation induces a unique and rare golden lustre property, which was not inherent to the ligand itself and shows potential for future application.
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ProQuest PhD and Master's Theses International Dissemination Agreement
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This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.