The relationship between intermolecular interactions and charge transport properties of trifluoromethylated polycyclic aromatic hydrocarbons

•Relationship between intermolecular interactions and charge transport properties.•Intermolecular π-stacking interactions have much effect on the hole transport.•Hydrogen bonding interactions are mainly responsible for the electron transport.•A competitive relationship occurs between π-stacking and HB interactions.

Polycyclic aromatic hydrocarbons (PAHs) with the electron-withdrawing groups such as halogen atom, cyanide, perfluoroalkyl (PFA), or perfluoroary, etc. exhibit good air stability and better solid-state charge carrier mobility. To obtain a better understanding of structure property relationships of this kind of compounds, a series PAH(CF3)n derivatives a1, a2, b1, b2, c1, and c2, which contain different numbers of trifluoromethyls and benzene rings, were chosen and studied by both band-like model and hopping model. Their crystals contain different intermolecular interactions. It turns out that intermolecular hydrogen bonding interactions are mainly responsible for electron transport, while π-stacking interactions dominate hole transport. When the π-stacking and intermolecular hydrogen bonding interactions coexist in the same direction, a competitive relationship occurs between hole and electron transport, which tend to cause enhancement of electron transport, and restrain hole transport.

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