Optoelectronic and conductivity of ᴫ‐conjugated polymers based on phenylenevinylene, 1,3,4‐thiadiazole and thiophene: Suitable candidates for n‐type organic semiconductors

New poly‐phenylenevinylenes PPVs containing 1,3,4‐thiadiazole as candidates for organic semiconductors have been theoretically studied at density functional theory (DFT) and time‐dependent DFT levels. This study has been conducted in order to investigate the geometrical and electronic properties as well as the conductivity of a series of PPV–thiophene–1,3,4–thiadiazole–thiophene (H–PhTAT–H) containing –CHO, –CH₂–P(=O)(OCH₃)₂, and phenyl–CHO (PhCHO) terminal groups. The impact of terminal groups on the optical bandgaps, electron affinity, LUMO energy, and intramolecular reorganization energy was studied for different oligomers and for a limit polymer. The incorporation of terminal groups did not affect the chain length evolution and the vertical transition energy E_vert value for a polymer limit compared with the unsubstituted oligomer (H–PhTAT–H). All studied properties showed that CHO–PhTAT–PhCHO and H–PhTAT–H oligomers can be considered as n‐type semiconductors.