Theoretical study on the relationship between the molecular structures and optoelectronic properties of aromatic-fluorinated sumanene derivatives

Aromatic-fluorinated sumanene derivatives have been designed and studied systematically using DFT and TDDFT methods. The geometric structures, frontier molecular orbitals, ionization potentials, electron affinities, reorganization energies, absorption spectra, fluorescence emission spectra, radiative decay rates, non-radiative decay rates and fluorescence quantum yields of the molecules have been discussed by comparison. The results show that 2,5,8-trifluorosumanene (8) should be especially beneficial to charge transport rather than fluorescence emission. Besides, 3,5-difluorosumanene (5), 2,3,6-trifluorosumanene (7) and 2,3,6,8-tetrafluorosumanene (13) should be more beneficial to charge transport and fluorescence emission than their respective isomers. In addition, the mono-substituted sumanenes could be designed as good optoelectronic materials more easily than other sumanene derivatives. In a word, the relationship between the molecular structures and optoelectronic properties of aromatic-fluorinated sumanene derivatives has been established by calculation, which can provide a theoretical reference for the experimental design of novel bowl-shaped organic optoelectronic materials based on aromatic-substituted sumanene derivatives.