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.

The fuzzy frontiers between structure determination by powder diffractometry and crystal structure prediction are discussed. The application of a search-match program combined with a database of more than 60 000 predicted powder diffraction patterns is demonstrated. Immediate structure solution (before indexing) is shown to be possible by this method if the discrepancies between the predicted crystal structure cell parameters and the actual ones are <1%. Incomplete chemistry of the hypothetical models (missing interstitial cations, water molecules, etc.) is not necessarily a barrier to a successful identification (in spite of inducing large intensity errors), provided the search-match is made with chemical restrictions on the elements present in both the virtual and experimental compounds.