Bromination and cyanation for improving electron transport performance of anthra-tetrathiophene

The charge transport properties of anthra-tetrathiophene (ATT) and its brominated and cyanated derivatives (TBATT and TCATT) were investigated by the density functional theory (DFT) coupled with incoherent charge-hopping model. The crystal structure of TCATT is predicted by the dispersion-corrected DFT (DFT-D) method, and those of ATT and TBATT are retrieved from the Cambridge Crystallographic Data Center. The introduction of electron-withdrawing substituents of bromine and cyano decreases the frontier molecular orbital energies but increases the electron affinities, which is beneficial to electron injection and guarantees charge carrier stabilization. The π-π stacking of neighbor molecules with a short distance and large coupling area contributes to the largest transfer integral. The predicted electron mobility of TCATT reaches up to 1.851 cm2/(V·s), indicating that the cyanation of ATT is favorable for improving the electron transport. The angular dependent simulation for electron mobility shows that the electron transport is remarkably anisotropic.