Studies on heteroporphycene synthesis

Abstract

Chapter one of this thesis gives an overview of light-matter interactions, organic photochemistry and two-photon absorption spectroscopy. Conceptual beginnings of the project are discussed and target compounds for synthesis are identified through computational studies.

Chapter two, section one outlines the efforts to synthesise dioxaporphycene porphycene targets through crossed McMurry coupling reactions. Contained are novel crossed porphycene compounds as well as a newly discovered macrocycle containing both furan and sulfur functionality, the structure of which was characterised crystallographically. The crossed McMurry reaction is rationalised computationally, where we identify a key factor for a compatible cross-coupling partner. The efforts contained in this section have been published in the European Journal of Organic Chemistry.

Chapter two, section two describes the substantial steps taken to synthesise a new carbazole structure as a precursor compound to porphycene macrocycles. The chapter contains key novel structures which led to the direct precursor target and discusses the synthetic methods used to reach the final structures.

Chapter two, section three describes an alternative synthetic route towards porphycene macrocycles, via a stepped approach to build complex functionality from common starting materials.

Chapter two, section four describes the contributions made towards the group project on intramolecular nitrofuran Diels-Alder reactions and the counter intuative rate enhancement observed by the introduction of the nitro-group. A computational study of the effect is contained and the effect is rationalised in the discussion. A summary of the research contained in this section has been published in the Journal of Organic Chemistry.

Chapter three, contains experimental details of all the novel compounds produced in the research chapters along with details of synthetic improvements or alternative synthesis of known compounds.