Synthesis of carbazole-type D-π-A fluorescent dyes possessing solid-state red fluorescence properties

摘要

Carbazole-type donor-π-acceptor (D-π-A) fluorescent dyes (SO1 and SO2), each containing a diphenylamino system as an electron-donating group and a nitro moiety as an electron-accepting group, have been designed and synthesized, and their photophysical properties in solution and in the solid state have been investigated. The absorption and fluorescence properties of SO1 and SO2 in solution are similar, and both dyes exhibited moderate fluorescence quantum yields. In the solid state, however, the dye SO2, with a butyl substituent on the carbazole ring, exhibited red fluorescence at around 620 nm, whereas the dye SO1, with no substituent on the carbazole ring, did not exhibit these solid-state fluorescence properties. Furthermore, the dye SO2 exhibited weak mechanofluorochromic (MFC) properties: grinding of as-recrystallized dyes induces slight bathochromic shifts of the fluorescence excitation and emission maxima. To elucidate the effects of molecular and crystal structures on the solid-state fluorescence properties, we performed semiempirical molecular orbital calculations (PM3 and INDO/S) and single-crystal X-ray structural analysis. The X-ray crystal structures of SO1 and SO2 demonstrated that a continuous intermolecular π-stacking between the fluorophores was observable in the crystal structure of SO1, but not in that of SO2. The MO calculations revealed that SO1 and SO2 have similarly large dipole moments in the ground state (μ _g ≈ 8 D). The relationship between the observed solid-state photophysical properties and the molecular and crystal structures of the carbazole-type D-π-A fluorescent dyes are discussed on the basis of experimental results and MO calculations. It is found that the formation of a continuous intermolecular π-stacking between the fluorophores causes a drastic fluorescence quenching in the solid state and that D-π-A fluorescent dyes with very large dipole moments can reduce the MFC properties, due to strong dipole-dipole interactions between the fluorophores in the solid state.