“Disrupt and induce” intermolecular interactions to rationally design organic semiconductor crystals: from herringbone to rubrene-like pitched π-stacking
Chengyuan Wang, Daisuke Hashizume, Masahiro Nakano, Takuya Ogaki, Hiroyuki Takenaka, Kohsuke Kawabata, Kazuo Takimiya
Abstract
The packing structures of organic semiconductors in the solid state play critical roles in determining the performances of their optoelectronic devices, such as organic field-effect transistors (OFETs). It is a formidable challenge to rationally design molecular packing in the solid state owing to the difficulty of controlling intermolecular interactions. Here we report a unique materials design strategy based on the β-methylthionation of acenedithiophenes to generally and selectively control the packing structures of materials to create organic semiconductors rivalling rubrene, a benchmark high-mobility material with a characteristic pitched π-stacking structure in the solid state. Furthermore, the effect of the β-methylthionation on the packing structure was analyzed by Hirshfeld surface analysis together with theoretical calculations based on symmetry-adapted perturbation theory (SAPT). The results clearly demonstrated that the β-methylthionation of acenedithiophenes can universally alter the intermolecular interactions by disrupting the favorable edge-to-face manner in the parent acenedithiophenes and simultaneously inducing face-to-face and end-to-face interactions in the β-methylthionated acenedithiophenes. This "disrupt and induce" strategy to manipulate intermolecular interactions can open a door to rational packing design based on the molecular structure.