6,13-Substituted pentacenes are accessible through pentacenequinone by reaction with an aryl or alkynyl nucleophile (for example Grignard or organolithium reagents) followed by reductive aromatization. Another method is based on homologization of diynes by transition metals (through zirconacyclopentadienes) Functionalization of pentacene has allowed for control of the solid-state packing of this chromophore. The choice of the substituents (both size and location of substitution on the pentacene) influences the solid-state packing and can be used to control whether the compound adopts 1-dimensional or 2-dimensional cofacial pi-stacking in the solid-state, as opposed to the herringbone packing observed for pentacene.