Organic electronic devices are becoming commonplace in many academic and industrial materials laboratories, and commercial application of these technologies is underway. To maximize our fundamental understanding of organic electronics, a wide array of molecular frameworks is necessary, as it allows for a variety of optical and electronic properties to be systematically investigated. With the ability to further tune each individual scaffold via derivatization, access to a broad spectrum of interesting materials is possible. Of particular interest in the search for organic semiconducting materials are the cyclopenta-fused polyaromatic hydrocarbons, including those based on the fully conjugated indenofluorene (IF) system, which is comprised of five structural isomers. This dissertation represents my recent contributions to this area of research. Chapter I serves as a historical perspective on early indenofluorene research and a review of more current research on their synthesis and applications in organic electronic devices. Chapters II and III cover our early work developing the synthesis of the fully-reduced indeno[1,2-b]fluorene scaffold, with the latter of these chapters showing the first example of its application in an organic electronic device, a field effect transistor. Chapter IV demonstrates the first syntheses of fully-reduced indeno[2,1-c]fluorene derivatives. Chapter V expands our research to encompass isoelectronic heteroatomic derivatives of that same scaffold, introducing the fully-reduced diindeno[2,1-b:1',2'-d]thiophene scaffold and showing that our synthetic methodology also can be used to produce a quinoidal thiophene core. Chapter VI concludes with a review of the similarities between the indeno[2,1-c]fluorene and diindeno[2,1-b:1',2'-d]thiophene molecular architectures and introduces benzo[a]indeno[2,1-b]fluorene derivatives, demonstrating the first example of a fully-reduced indenofluorene that possesses a non-quinoidal core, illustrating that the quinoidal core is not a prerequisite for the strong electron affinities seen across the families of fully-reduced indenofluorenes. This dissertation encompasses previously published and unpublished co-authored material. / 2015-10-10