Diselenophene‐Dithioalkylthiophene Based Quinoidal Small Molecules for Ambipolar Organic Field Effect Transistors

Abstract This work presents a series of novel quinoidal organic semiconductors based on diselenophene‐dithioalkylthiophene (DSpDST) conjugated cores with various side‐chain lengths (‐thiohexyl, ‐thiodecyl, and ‐thiotetradecyl, designated DSpDSTQ‐6, DSpDSTQ‐10, and DSpDSTQ‐14, respectively). The purpose of this research is to develop solution‐processable organic semiconductors using dicyanomethylene end‐capped organic small molecules for organic field effect transistors (OFETs) application. The physical, electrochemical, and electrical properties of these new DSpDSTQs are systematically studied, along with their performance in OFETs and thin film morphologies. Additionally, the molecular structures of DSpDSTQ are determined through density functional theory (DFT) calculations and single‐crystal X‐ray diffraction analysis. The results reveal the presence of intramolecular S (alkyl)···Se (selenophene) interactions, which result in a planar SR‐containing DSpDSTQ core, thereby promoting extended π‐orbital interactions and efficient charge transport in the OFETs. Moreover, the influence of thioalkyl side chain length on surface morphologies and microstructures is investigated. Remarkably, the compound with the shortest thioalkyl chain, DSpDSTQ‐6, demonstrates ambipolar carrier transport with the highest electron and hole mobilities of 0.334 and 0.463 cm2 V−1 s−1, respectively. These findings highlight the excellence of ambipolar characteristics of solution‐processable OFETs based on DSpDSTQs even under ambient conditions.