“Manipulation” of Crystal Structure by Methylthiolation Enabling Ultrahigh Mobility in a Pyrene‐Based Molecular Semiconductor

Control and prediction of crystal structures molecular semiconductors are considered challenging, yet they crucial for rational design superior semiconductors. It is here reported that through methylthiolation, one can rationally control the structure pyrene derivatives as semiconductors; 1,6-bis(methylthio)pyrene keeps a similar sandwich herringbone to parent pyrene, whereas 1,3,6,8-tetrakis(methylthio)pyrene (MT-pyrene) takes new type brickwork structure. Such changes in these explained by alteration intermolecular interactions efficiently controlled methylthiolation. Single crystals MT-pyrene evaluated active semiconducting material single-crystal field-effect transistors (SC-FETs), which show extremely high mobility (32 cm2 V−1 s−1 on average) operating at drain gate voltages −5 V. Moreover, band-like transport very low trap density experimentally confirmed SC-FETs, testifying among best SC-FET devices.