Acenes have emerged as an important class of organic electronic material. Related heteroatom-substituted compounds, or heteroacenes, introduce an important means for modulating properties and improving materials' stability. In this perspective, we will review the historical origins of the heteroacenes and discuss recent progress in the field of acene and related compounds containing fused 1,4-diazabenzene units, i.e. pyrazine, also known as the 'pyrazinacenes'. We focus not only on the types of materials that have been prepared but also on their chemical and physical properties, including synthetic procedures, electronic properties, self-assembly characteristics, and we also introduce some of the computational studies aimed at understanding the more unusual behaviours of this group of compounds, such as protic tautomerism and aromaticity/ antiaromaticity.
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