We present a structural and electronic inspection of reduced pyrazinacenes within the DFT framework. Our analysis provides a clear indication that compounds in which reduced pyrazine rings are well separated from each other are rather stable. Conversely, if the reduced pyrazine rings approach each other or cluster together, the compounds become increasingly unstable. The tautomers analyzed are likely to possess properties suitable for application as proton transport materials due to protic isomerism processes. On the basis of our findings, we propose that protic transport should occur through a concerted proton transfer without involving intramolecular aggregation of the dihydropyrazine groups. Furthermore, the electronic structure analysis shows that this class of compounds can be classified as small bandgap semiconducting materials, possessing even metallic character depending on the tautomeric structure, and with potential nanotechnological applications in molecular electronics and fuel cells.