Fused Thiophene‐Pyrrole‐Containing Ring Systems up to a Heterodecacene

A new class of π-conjugated polycyclic hydrocarbons that promises interesting electronic properties is presented. The synthesis and extension of the S,N-heteroacene series consisting of only five-membered heterocyclic rings up to a very long, stable, and still soluble decacene SN10 is realized by multiple Pd-catalyzed aminations of halogenated thiophene precursors as key reactions. These novel heteroacenes were characterized by optical spectroscopy and electrochemistry providing interesting structure-property relationships. Nearly complete bond-length equalization in the inner part of the conjugated backbone and an unusual herringbone packing in the solid state underline the structural features of these novel systems.