Enhancing charge mobilities in organic semiconductors by selective fluorination: a design approach based on a quantum mechanical perspective† †Electronic supplementary information (ESI) available: Reorganization energy, orbital-based coupling energies, HRFs, normal mode motions, transfer rates, and atomic coordinates. See DOI: 10.1039/c7sc02491f Click here for additional data file.

Selective fluorination of organic semiconducting molecules is proposed as a means to achieving enhanced hole mobility. Naphthalene is examined here as a root molecular system with fluorination performed at various sites. Our quantum chemical calculations show that selective fluorination can enhance attractive intermolecular interactions while reducing charge trapping. Those observations suggest a design principle whereby fluorination is utilized for achieving high charge mobilities in the crystalline form. The utility of this design principle is demonstrated through an application to perylene, which is an important building block of organic semiconducting materials. We also show that a quantum mechanical perspective of nuclear degrees of freedom is crucial for a reliable description of charge transport.