Functional Dithienopyrazines: Structure‐Property Relationships**

Dithienopyrazines are only scarcely used as building blocks in organic electronic materials. Here, we report efficient preparation and investigation of syn‐ and anti ‐dithienopyrazines, which were functionalized with triaraylamine units to provide different series of donor‐acceptor‐donor‐type materials. The characterization of the optoelectronic properties resulted in valuable structure‐property relationships and allowed for the elucidation of the influence of structural effects such as core structure ( syn vs anti ), type of substituents (directly arylated vs ethynylated aryl), and substitution pattern (α,α’‐ vs β,β’‐ vs fourfold substitution). Finally, first application of a dithienopyrazine derivative as model for hole‐transport materials tailored for organic electronic devices has been realized.