Crystal-Structure Simulation of Methylthiolated Peri-Condensed Polycyclic Aromatic Hydrocarbons for Identifying Promising Molecular Semiconductors: Discovery of 1,3,8,10-tetrakis(methylthio)peropyrene Showing Ultrahigh Mobility

The crystal structures of molecular semiconductors critically affect their carrier-transport properties. One of the promising crystal structures that afford high carrier mobility is a brickwork structure recently reported for 1,3,6,8-tetrakis(methylthio)pyrene (MT-pyrene) showing ultrahigh mobility. However, such ultrahigh mobility is not realized in other methylchalocogenolated pyrenes, owing to subtle differences in the molecular positions in their crystal structures. This means that, for developing superior molecular semiconductors, it is desirable to simulate the crystal structure with sufficient quality before time-consuming and labor-intensive synthetic trials. To realize this, a new computational approach is developed to simulate crystal structures of all methylchalocogenolated pyrenes, which is then applied to MT-pyrene-related methylthiolated peri-condensed polycyclic aromatic hydrocarbons including perylene, peropyrene, and terrylene derivatives. Among these, 1,3,8,10-tetrakis(methylthio)peropyrene (MT-peropyrene) is expected to show high mobility based on the simulated crystal structures. Thus, MT-peropyrene is chosen as the synthetic target, and a new peropyrene synthesis method is developed. Thus synthesized MT-peropyrene has virtually the same crystal structure as the simulated one, and its single-crystal field-effect transistors show mobility as high as 30 cm(2) V-1 s(-1) and band-like transport behaviors. These results indicate that the present crystal-structure simulation is a powerful tool for exploring promising molecular semiconductors.