Dicyano- and tetracyanopentacene: foundation of an intriguing new class of easy-to-synthesize organic semiconductors.

Cyanated pentacenes are very promising candidate materials for ambipolar and n-type transistors. However, only a few examples have been obtained to date - all requiring lengthy, multi-step processes. Herein, we present the first preparation of 5,7,12,14-tetracyanopentacene (TCP) and a facile, scaled-up preparation of 6,13-dicyanopentacene (DCP). Both compounds are prepared by a one-pot synthesis using cheap quinones as starting materials. Detailed crystallographic investigations evince that the bulk assemblies of both cyanated pentacenes are dominated by non-covalent interactions, resulting in a dense, stable, face-to-face packing and in an intriguing packing motif for TCP. Very low frontier molecular orbital energy levels and a reversible bleaching of TCP are revealed by cyclic voltammetry. Finally, both cyanated pentacenes are used in proof-of-concept organic thin-film transistors (OTFTs) operating under ambient conditions. This work highlights the potential of cyanation for larger acenes and presents a straightforward route to the rational design of this promising class of materials.