Synthesis, optical and electrochemical properties of (D–π)(2)-type and (D–π)(2)Ph-type fluorescent dyes

The (D–π)(2)-type fluorescent dye OTT-2 with two (diphenylamino)carbazole-thiophene units as D (electron-donating group)–π (π-conjugated bridge) moiety and the (D–π)(2)Ph-type fluorescent dye OTK-2 with the two D–π moieties connected through a phenyl ring were derived by oxidative homocoupling of a stannyl D–π unit and Stille coupling of a stannyl D–π unit with 1,3-diiodobenzene, respectively. Their optical and electrochemical properties were investigated by photoabsorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, cyclic voltammetry (CV) and molecular orbital (MO) calculations. In toluene the photoabsorption and fluorescence maximum wavelengths (λ(max,abs) and λ(max,fl)) of OTT-2 appear in a longer wavelength region than those of OTK-2. The fluorescence quantum yield (Φ(fl)) of OTT-2 is 0.41, which is higher than that (Φ(fl) = 0.36) of OTK-2. In the solid state OTT-2 shows relatively intense fluorescence properties (Φ(fl-solid) = 0.24 nm), compared with OTK-2 (Φ(fl-solid) = 0.15 nm). CV results demonstrated that OTT-2 and OTK-2 exhibit a reversible oxidation wave. Based on photoabsorption, fluorescence spectroscopy and CV for the two dyes, it was found that the lowest unoccupied molecular orbital (LUMO) energy level of OTT-2 is lower than that of OTK-2, but OTT-2 and OTK-2 have comparable highest occupied molecular orbital (HOMO) energy levels. Consequently, this work reveals that compared to the (D–π)(2)Ph-type structure, the (D–π)(2)-type structure exhibits not only a bathochromic shift of the photoabsorption band, but also intense fluorescence emission both in solution and the solid state.