Azaacenes have been known for a very long time, either as N,N'-dihydro compounds or in their oxidized form as 4n+2π systems, but only recently have processable and charcterizable derivatives been sought. In the last three years synthetic routes to large N-heteroacenes have been developed. In particular, the Pd-catalyzed coupling of aromatic diamines with activated aromatic dihalogenides has enabled simple access to numerous new azaacenes. Since 2010, azapentacene and stabile oligoazahexacene have been synthesized, as well as a symmetrical tetraazapentacene, which acts as an excellent electron-transport material for thin-film transistors.

We describe the modular synthesis of three novel large N-heteroarenes, containing 9, 11, and 13 annulated rings. This modular system features fused azaacene units to a coronene nucleus. We evaluate the optical and electronic properties and the solid-state packing of the targets. The electronic properties of the 13-ring N-heteroarene allow the fabrication of a proof-of-concept thin-film transistor. Electron mobilities up to 8 × 10(-4) cm/(V s) were obtained for polycrystalline films.

Novel phenazinothiadiazoles were prepared by condensation of ortho-quinones and an alkynylated 5,6-diamino-2,1,3-4 benzothiadiazole and evaluated as transport materials in thin film transistors.

Two literature-known TIPS-ethynyl-dibromoacenes were prepared and employed to synthesize cyclotrimers by using Yamamoto coupling conditions. Two large, well-soluble starphenes were isolated in good yields. Crystallographic characterization verifies the triangular shape and shows significant differences in crystal packing.