An accurate prediction of oxidation potential for a series of phenylthiophene derivatives

A high-level composite G4 method was used to predict the oxidation potential of a series of 3-(para-X-phenyl)thiophenes (X= -CH3, -OCH3, -H, -F, and -C1). An excellent agreement was found between the calculated and experimental values. [Display omitted] •High-level composite G4 method was used to predict thermodynamic properties.•An excellent agreement was found between the theoretical and experimental Eox values.•Several correlations were obtained for Eox with various electronic characteristics.•Enthalpies of formation revealed an improvement in the thermodynamic stabilization of PTs.•Substituted-PT can play a fine-tune effect on the structure-energetics of poly(PT)s. The high-level composite G4 method is used to calculate the gas phase standard molar enthalpies of formation (ΔHf,298) for a series of 3-(para-X-phenyl)thiophenes (PTs), in which X is referred to as the -CH3, -OCH3, -H, -F, and -C1 substituents. The accurate oxidation potential (Eox) values are also calculated with respect to the Ag/AgCl reference electrode in acetonitrile. The results show that the theoretical and experimental Eox values are in excellent agreement with each other; these quantities successfully reveal a linear correlation with various electronic characteristics of PTs. A linear dependence behavior on the Hammett constants of the substitutions can be seen for the Eox values. Analysis of the HOMO-LUMO band gap and the UV–visible spectral properties demonstrate the facility of hole transport for the PTs as a potential candidate for conducting polymers.