Theoretical study of one-and two-photon absorption properties for three series of diphenylamine and difluorenylamine substituted conjugated compounds

摘要

The one-photon (OPA) and two-photon (TPA) absorption properties of three series of symmetrically substituted quadrupolar compounds with structure of donor-π bridge-donor (DπD) were investigated by time-dependent density functional theory (TDDFT) based on the HartreeFock (HF)-optimized geometrical structures. These compounds were constructed with either phenyl or fluorenyl groups connected by vinylene unit as the central π-conjugated bridges and either diphenylamine or difluorenylamine groups as terminal electron donors. The calculated OPA spectra are dominated by two strong transitions which are attributed to the charge transfers from the donor groups to central conjugated chains. The OPA and TPA transition strength all increase with the extension of conjugated chain length in each series and the corresponding wavelength shifts red in general. The transition strength in either OPA or TPA process also increases from series one to series two or three by replacing the phenyl groups with fluorenyl groups. The intramolecular charge transfers make significant contributions to the TPA activity. According to the three-state model, the enhanced TPA activity comes from the enhancement of transition moment between statesstates as conjugated chain increases.