Heteroaromatic molecules as supramolecular materials

Type of content
Theses / Dissertations
Publisher's DOI/URI
Thesis discipline
Chemistry
Degree name
Doctor of Philosophy
Publisher
University of Canterbury
Journal Title
Journal ISSN
Volume Title
Language
English
Date
2019
Authors
Bodman, Samantha
Abstract

This thesis describes the preparation of a series of novel heterocyclic aromatic compounds and investigation of their coordination chemistry with a range of different metals and counter ions. The target compounds require a variety of synthetic methods, including palladium cross-coupling reactions, Diels-Alder cycloadditions, photochemical cyclisation and nucleophilic addition, followed by reductive aromatisation. The overall aim of the work is to synthesise novel nitrogen-containing aromatic compounds to use in optoelectronic devices that have the ability to undergo singlet fission by controlling the distances between the chromophores through metallosupramolecular chemistry.

Chapter One outlines an introduction to the topics discussed in this study, providing examples from the literature. Chapter Two details the syntheses of 5,6-disubstituted-1,10- phenanthroline compounds and the corresponding coordination complexes with ruthenium(II), copper(I) and silver(I). The complexes have been characterised through solution studies and/or single crystal X-ray diffraction analyses. Photochemical cyclisation of 5,6-disubstituted complexes were attempted and subsequent computational studies were completed. Chapter Three describes the synthesis of pyridyl containing pentaphenylbenzene derivatives and attempts towards the photochemical cyclisation reactions for the formation of nitrogen- containing polycyclic aromatic hydrocarbons. Computational studies were also completed. Chapter Four investigates the synthetic development of acene derivatives with appended pyridyl substituents. The derivatives were complexed with a range of metal salts and the development of interesting polymer topologies and discrete structures with interesting intermolecular interactions are reported. Chapter Five details the synthesis and characterisation of acenaphthoquinone bridged and bidentate compounds and investigation of the coordination chemistry with ruthenium(II) and palladium(II). Chapter Six concludes the results as a whole and potential future directions of this work are presented. Chapter Seven outlines the synthetic routes along with the characterisation data of the new and modified syntheses of the ligands and complexes in this study.

Overall, twenty-six novel organic compounds and thirty new coordination complexes were prepared using a variety of synthetic routes during the course of this study and were characterised by single crystal X-ray diffraction analysis and spectroscopic techniques where appropriate. The topologies formed have given insight into potential singlet fissionable candidates to control the distance between the chromophores for implementation in photovoltaic devices.

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