Theoretical investigations of the substituent effect on the opto-electronic properties of the linearly fused napthadithiophene-based molecules.

The optoelectronic and charge transport properties of eight linearly fused Napthadithiophene (NDT) molecules with different electron-withdrawing (EWG) and electron-donating (EDG) substituents are studied using the density functional theory (DFT) methods. The effect of the substitution of EWG and EDG on the molecular structure, frontier molecular orbitals, ionization energy, electron affinity, reorganization energy, crystal packing, and charge carrier mobility are studied. The crystal structure simulation method is used to optimize the possible crystal packing arrangements for the studied molecules. The energy and distribution of electron density on the frontier molecular orbitals are strongly influenced by the substitution of EWG and EDG, thereby changes in the absorption spectrum and charge transport properties. The unsubstituted NDT molecule possesses a maximum hole mobility of 2.8 cm2 V-1 s-1, which is due to the strong intermolecular interactions. Therefore, the NDT molecule can be used as a p-type semiconducting material. Among the studied molecules, the CCH-substituted NDT molecule, NDT-CCH, possesses a higher electron mobility of 1.13 cm2 V-1 s-1. The C2H5-substituted NDT molecule, NDT-C2H5, possesses ambipolar behavior with mobility of 4.77 × 10-2 cm2 V-1 s-1 and 1.70 × 10-2 cm2 V-1 s-1 for hole and electron, respectively.