Ab initio calculations of the molecular structure and vibrational frequencies of fluorinesubstituted pyrroles

In this work, the structural, electronic and energetic properties of neutral and singly ionized flouromethylpyrroles(FMPs) were carried out by means of Hartree-Fock (HF) and B3LYP-DFT methods. The characterization ofthe titled molecules was discussed and rationalized in term of the number and position of the fluorine atoms. Thecalculations were performed on the mono-, di-, and tri-fluorosubstitued methyl-pyrroles by employing the B3LYP/6-31G(d,p) level of theory. The results obtained reveal that the fluorine-substituted methyl groups play a fine-tune effecton the properties of the FMT monomers. It is found that the electronic properties can be successfully correlated withthe electronic character of the substitution via a linear dependence behavior on the Hammet function. Moreover, thefrontier molecular study reveals that the p- and n-doped states had more suitable properties respect to un-substitutedpyrrole, reflecting the hole and electron transport characteristics of the FMT derivatives. It was found thatcharacteristics of the fluorinated substitutions in these molecules have important role in the polymerization process andtheir polymer products. We hope that the results obtained can be helpful in designing a series of modified materialswith the facility of hole and electron injections and the efficient charge transport.