Poly(arylenethynyl-thienoacenes) as candidates for organic semiconducting materials. A DFT insight

► HOMO/LUMO energies, IP, EA and λi show a progression with aryl and thieno-acene sizes. ► μhop+/μhop- ratio points most of ArCCTxs show either a stronger p- or n-character. ► F/CN motifs on ArCCT1 make hole/electron mobilities to increase in a balanced way. ► PhCCT1CN/FArCCT1F show hole and electron injections from Au electrode. ► Also, they show high hole and electron mobilities and μhop+/μhop-≃1.