I will present our synthetic, structural and materials studies of a new class of electron-accepting molecules based on the indenofluorene (IF) skeleton. The initial preparative route involved transannular cyclization of dehydroannulenes to afford the pentacyclic ring system. Subsequent transformations generated the first stable examples of the fully conjugated, 20 pi-electron, formally anti-aromatic compounds. Optimization of intermediate IF-6,12-dione synthesis via a simple three-step process now permits access to IF derivatives in multigram quantities. Work on 6,12-diarylIFs demonstrated that single crystals of the pentafluorophenyl derivative could serve as an active layer in organic field effect transistors (OFETs) that exhibit ambipolar behavior using Au source/drain contacts. Current studies are focused on replacement the benzene groups with heterocyclic units such as thiophene, as well as expansion of the central quinoidal motif. This presentation will showcase the latest results from our lab.