Characteristics of new pyrrolic derivatives and their oligomers using DFT and TD-DFT calculations.

Abstract

This article is based on the study of pyrrolic derivatives and their oligomers. Knowing that, pyrrolic derivatives are widely studied on an industrial scale. The aim of this work is to find pyrrolic derivatives having the same physicochemical characteristics such as the pyrrolic edifice. Six derivatives were studied by substituting the hydrogens in the β position of the pyrroles with the following radicals: -CHO, -Cl, -CN, -NO, and -OH. The study was carried out theoretically using ab initio and density functional of theory (DFT) methods. In the first step, molecules of four units were taken into consideration in order to make the comparison between them. This comparison showed that the majority of molecules exhibited high intramolecular charge transfer (ICT) compared to the molecule composed of four pyrrolic units (OP4), and also exhibited strong nucleophilic and electrophilic characteristics. Natural bond orbital (NBO) analysis has shown continuous ICT mechanisms for certain molecules. The studied derivatives showed good solvation in several solvents compared to OP4. The molecules substituted by the radicals -CHO, -CN, -OH, and -NO generated several peaks in the excited states, which is the opposite case for the other molecules with a single peak. The effects of chain elongation revealed exponential equations generated by the two parameters energy gaps (ΔEH-L) and maximum wavelengths (λmax) as a function of the number of units (n). These equations were used to predict the maximum and minimum values of the above parameters for more elongated oligomers. The software used to make the calculations is Gaussian 16. All geometries were calculated by B3LYP functional and 6-31++G(d,p) basis set. The electronic parameters ΔEH-L were calculated by the following functionals: B3LYP, CAM-B3LYP, LC-wPBE, LC-BLYP, wB97X, M062X, M06HF, and M11 in addition to the second-order Møller-Plesset method (MP2) while always keeping the basis set mentioned before. An effect of basis set variation was studied by the optimal functional in combination with the following basis sets: 6-31G(d,p), 6-31++G(d,p), cc-pVDZ, AUG-cc-pVDZ, 6-311G(d,p), 6-311++G(d,p), cc-pVTZ, and AUG-cc-pVTZ. The NBO study was carried out with the M06HF/6-31++G(d,p) functional using the NBO method. The solvation parameters were calculated by M06HF/6-31++G(d,p) in the presence of the implicit solvation model Solvation Model based on Density (SMD). The excited states were calculated by M06HF/6-31++G(d,p) by the implicit solvation model Conductor Polarizable Continuum Model (CPCM).