Innovative Organic Electroluminescent Materials with a Doublet Ground State：a Theoretical Investigation.

The displaced and distorted harmonic oscillator model, which has been proven to be appropriate in calculating vibronic spectra, is employed to treat the emission spectrum of title molecules in combination with a thermal vibration correlation function. The calculated results indicate that the main peak of the emission spectrum is visibly impacted by the normal modes with lower frequencies and that the shoulder peak is originated from the middle-frequency modes. On the level of time-dependent density functional theory (TDDFT), the calculated fluorescence lifetimes of TTM-3NCz and TTM-3PCz are 22.1 and 26.0 ns, respectively, which happen to coincide with the observed values of TTM-3NCz (17.2 ns) and TTM-3PCz (21.2 ns). The above data indicate that both the calculated radiative decay rates are reasonable at room temperature. Furthermore, we investigate the influence of the Duschinsky effect on the fluorescence quantum efficiency (FQE). When it is considered, the predicted FQE of the TTM-3NCz molecule is only 0.11%, and the observed value (49% in toluene) deviates significantly. If we ignore the Duschinsky effect, the FQE of TTM-3NCz increases dramatically to 41.8%. For the TTM-3PCz molecule (the FQE is 46% in toluene), the calculated FQE is 0.042% with the Duschinsky effect and increases to 45.2% without the Duschinsky effect. This phenomenon might be related to external factors and the nature of the TDDFT only considering a single configuration. In addition, the fluorescent properties of the fluorinated TTM-3NCz molecules are studied predictably. The obtained results show that the perfluorinated TTM-3NCz shows better luminous performance due to larger oscillator strength. Finally, the dimers, which are composed of both single title molecules, are explored theoretically to determine how they impact the fluorescent property; however, the effect can be nearly eliminated because of the small binding energies.