In recent years, there has been tremendous interest in highly conjugated polycyclic hydrocarbons, such as the higher acenes, because of their fascinating optical and electronic properties. Although pentacene and its derivatives have been utilized in device applications such as field effect transistors, photovoltaics, and light emitting diodes, these molecules are susceptible to oxidative and photolytic degradation; therefore, alternative, acene-like topologies must be investigated. Since 2010, our lab has been investigating isomers of an underexplored class of highly conjugated pentacyclic hydrocarbons known as indenofluorenes (IFs). The inclusion of the two five-membered rings in the indenofluorene core imparts an intrinsic ability to reversibly accept up to two electrons, making these molecules attractive as potential n-type materials. Recently, we disclosed the synthesis and characterization of several new thiophene-containing IF variants (indacenedithiophene and diindenothiophene).. Here, we report on the optical, electrochemical and solid-state characterization of several new benzofused derivatives (indacenedibenzothiophene) including several fluorinated examples, as well as extension to selenophene-containing molecules (indacenediselenophene and diindenoselenophene). Additionally, we have developed a broad synthetic methodology for the assembly of asymmetrically substituted indenofluorene analogues and herein divulge the synthesis, optical, electrochemical and solid-state characterization of two benzo[5,6]-s-indaceno[1,2-b]thiophene derivatives.