Quantum chemical studies on polythiophenes containing heterocyclic substituents: effect of structure on the band gap

Color tuning by the tailoring of substituents at the 3-position of thiophene is very encouraging, and comparative experimental and theoretical studies proved to be powerful in the search for a suitable design for the above. Since the novel polythiophene-based materials substituted with five-membered/six-membered ring containing sulphur and nitrogen at different positions are proven to be potential candidates for electron-transporting hole blocking functions, the structure-property relationship of these systems have been focused in the present study. Molecular-orbital calculations are applied to obtain the optimized geometries and band gaps of the thiophene oligomers. An oligomeric approach has been implemented for calculating the band gaps, and the theoretically obtained band gaps for the different model compounds are compared. Density-functional theory B3LYP∕6-31G∗ predicted band-gap values are compared with the experimental band gaps obtained from optical-absorption edge. The predicted values show little deviations from experimental band gaps, but the trend in band gap is found to be the same in experimental and theoretical results in most of the cases. Hence, this study illustrates the usefulness of quantum-mechanical calculations in understanding the effects of various structural parameters on optical band gap