Crystal-structure simulation of molecular semiconductors: brickwork-related crystal structures of methylthiolated peri-condensed polycyclic aromatic hydrocarbons†

Despite the critical importance to carrier transport properties, studies on the control and prediction of crystal structures of molecular semiconductors have not been well-matured. To tackle this issue, we have developed “in silico crystallization” (ISC) protocols for simulating the brickwork (BW) crystal structures of methylchalcogenolated polycyclic aromatic hydrocarbons (PAHs). In this study, by carefully analyzing a BW-related polymorph of experimental crystal structures, an inclined brickwork (iBW) structure, we further extend the ISC protocol to simulate various BW-related crystal structures including iBW structures. Rational conditional branching in the simulation not only makes it possible to simulate eight polymorph candidates of methylchalcogenolated PAHs but also helps understand the relationship between the polymorphs. Furthermore, the relative favorability of each polymorphic candidate, i.e., the likelihood of the appearance among the polymorph candidates, can also be evaluated.