Document Type


Degree Name

Doctor of Philosophy (PhD)



Program Name/Specialization

Biological and Chemical Sciences


Faculty of Science

First Advisor

Dr. Kenneth Maly

Advisor Role


Second Advisor

Dr. Louise Dawe

Advisor Role



Functional π-materials involve the use of an aromatic π-system to carry out a function such as electron transport (organic electronics), absorbing and emitting photons (dyes, fluorescent materials), self-assembly (discotic liquid crystals), or sensors for various analytes. Our lab has recently published the syntheses of heteroaromatic derivatives of tetrafluoroterephthalonitrile (TFTP, 2.24) synthesised via nucleophilic aromatic substitution chemistry. The prepared derivatives have displayed fluorescent (e.g. 2.2)1 and liquid crystalline (1.0)2 properties, as well as displaying close π-π interactions in the solid state (2.8).3 As the materials we are synthesising all belong to the class of aromatic compounds, an introduction to aromaticity and aromatic compounds, as well as an overview of the applications of this class, will be carried out in Chapter 1. Recently, we have focussed our attentions to modifications of the aromatic cores of such compounds and have synthesised a series of luminescent N–arylated derivatives, compound 2.17 being one such example. In addition to studying their photophysical properties, viz. absorbance and fluorescence spectroscopies, we have also grown adequate single crystals for X–ray diffraction analysis to study their solid–state organisation. The synthesis and properties of this series of N–aryl heteroacene analogues will be covered in Chapter 2. Furthermore, in our attempts to further modify the cores of our heteropentacene analogues, and attempt to generate materials possessing thermally-activated delayed fluorescence, we have turned our attention to the smaller congeners of the series. In addition to producing dibenzodioxin derivatives such as 3.22 which, like their larger cousins, display intense fluorescence in solution and solid states, we have happened across an unexpected ring opening reaction of the tetraoxapentacenes (such as 1.0) which leads to intriguing molecular architectures such as 3.31. The solid–state structures of these and other such compounds are discussed in Chapter 3. Finally, during the course of this work, a novel chemiluminescent reaction that involves aromatic compounds such as 2.8 or 2.24 with organic hydroperoxide anions was serendipitously discovered. Our efforts towards uncovering and understanding this unique reaction mechanism are delineated in Chapter 4.

Convocation Year


Convocation Season


Available for download on Friday, October 18, 2024