A DFT study on the photoelectric properties of rubrene and its derivatives.

The way to obtain new materials was usually to introduce some groups to molecules. Correlations among the molecular structure and photoelectric properties of rubrene and its eight derivatives have been studied in this paper, and the influences of the introduction of different electron-donating and withdrawing substituents on the molecular orbital, reorganization energies, absorption spectra, and fluorescence spectra of rubrene and its derivatives were discussed. In the present work, density functional theory calculations were performed at the B3LYP/6-311G(d,p) level to optimize the structure, and TD-DFT was used to calculate the absorption and emission spectra. Quantum chemistry calculation results indicated that the maximum absorption wavelengths are redshifted due to the introduction of cyclopentadienyl or furan groups, the maximum absorption wavelengths are blueshifted while methoxy groups substituted on tetracene backbone. We also discussed the influence of substituents on the molecule structure, which suggests that introducing furan and cyclopentadienyl substituents on the tetracene backbone can increase the rigidity of rubrene and improve the fluorescence intensity. The results of reorganization show that the introduction of cyclopentadienyl or furan groups into rubrene is advantageous to the holes transportation, and the introduction of F groups contributes to the electrons transportation. This study provides an insight into the properties of rubrene and its derivatives and supplies an effective method to design new organic semiconductor materials.