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Synthesis and Characterization of Cross-Conjugated Macrocycles and Exploratory Study of their Organometallic Chemistry Open Access


Other title
Type of item
Degree grantor
University of Alberta
Author or creator
Gholami, Mojtaba
Supervisor and department
Tykwinski, Rik R. (Chemistry Department)
Examining committee member and department
Hicks, Robin, G. (Chemistry Department, University of Victoria
Takats, Josef (Chemistry Department)
Stryker, Jeffery, M. (Chemistry Department)
McCaffrey, William, C. (Chemical and Materials Engineering Department)
Harynuk, James (Chemistry Department)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
This thesis covers the synthesis, characterization and physical studies of cross-conjugated macrocycles, expanded radialenes, as well as their related derivatives. The main synthetic protocol that is used throughout this thesis is based on the Pd-mediated Sonogashira cross coupling reaction of a desilylated iso-polydiacetylene with a dibromoolefin. To initiate the synthesis, a series of [3]–, [4]–, and [5]expanded radialenes was synthesized, characterized, and studied by UV-vis spectroscopy, electrochemistry, and solid-state analysis. The results confirm the macrocycles are achievable in reasonable yields and suitable for further physical studies without any concerns for their stability in the solid or solution phase. At the same time, the use of tetrabromoethene in analogous Sonogashira cross coupling reactions afforded bisexpanded radialenes and radiaannulenes that exhibited interesting physical properties according to UV-vis spectroscopy and cyclic voltammetric analysis. This thesis also covers some interesting results, in particular, for [3]expanded radialenes that undergo cycloaddition reactions. As well, physical studies of the target radialenes show that as the macrocycles become more strained, they exhibit more unique and unexpected electronic and optical properties. Having the first series of the radialenes in hand, the synthetic plan shifted towards the synthesis of functional expanded radialenes, which were produced in good to very good yields. In particular, the existence of a [4]expanded radialene carrying triisopropylsilylethynyl groups as exocyclic substituents provided an opportunity for derivatization of the expanded radialene framework. The general protocol for radialene synthesis was also applied using tetrabromides of anthracenylidene and pentacenylidene in Sonogashira reactions. These efforts afforded structurally unique bisexpanded radialene and radiaannulene products. Because of their shape and structure, radialenes have potential for use in organometallic chemistry or as ligands in inorganic chemistry. Exploratory studies have been focused on [3]– and [4]expanded radialenes. By all accounts, [3]radialenes reacted more easily with selected precursors such Pt(PPh3)4 and Co2(CO)8. Throughout this thesis, all the major radialene frameworks are established in terms of solid-state structures by X-ray crystallography. Finally, electrochemical analyses show that the new series radialenes reported in this work are generally reduced at higher potentials when compared to the previous generation of expanded radialenes based on butadiynyl building blocks.
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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