Design, Synthesis and Properties of Diindeno-Fused Acenes: Open-Shell Compounds for Organic Electronic Applications
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The consequence of free electrons in organic compounds has intrigued chemists for over a century. The fundamental idea of a covalent bond, a pair of electrons in a lasting attraction, and the localized spin of traditional stable free radicals are merged in biradical polycyclic hydrocarbons (PCHs). The field of open-shell PCHs has seen resounding growth over the last decade owing to the development of new synthetic methods, spectroscopic techniques and close collaboration between organic, physical and computational chemists. Previously inaccessible compounds have been shown possess useful electronic properties and the practical application of these new materials is only beginning to be explored. In this thesis I present the design, synthesis and application of the diindeno-fused acene class of biradical PCHs. In Chapter I recent work in the field of cyclopenta-fused PCHs, including indenofluorenes and diindenothienoacenes, is reviewed. Chapter II represents the first foray into expanding the (hetero)acene core of the diindenoacene family. Chapter III reports the synthesis and properties of an air-stable open-shell diindenoanthracene (DIAn) derivative. Chapter IV examines the redox chemistry of the DIAn system. In Chapter V I report the development and synthesis of a key advanced intermediate in the pursuit of new DIAn derivatives. This dissertation contains previously published and unpublished coauthored material.