Synthesis, Electrochemical, and Optical Properties of New Fluorescent, Substituted Thieno[3,2-b][1]Benzothiophenes

The synthesis, electrochemical and optical properties of three fluorescent substituted thieno[3,2-b][1]benzothiophenes (TBT) derivatives, including 3-methoxythieno[3,2-b][1]benzothiophene (3-MeO-TBT), 2,3-dimethylthieno[3,2-b][1]benzothiophene (2,3-diMe-TBT), and 6-methoxythieno[3,2-b][1]benzothiophene-2-carboxylate (6-MeO-TBT-2-COOMe), were investigated. The oxidation potential values varied between 1.40 and 1.20 V/SCE according to the electronic substituent effect, and electropolymerization attempts, performed in 0.1 M LiClO4 acetonitrile solution, led to the formation of very thin films of poly(3-MeO-TBT) and poly(2,3-di-Me-TBT). Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) , lifetimes (τF), and other photophysical parameters of the three new TBT derivatives were measured in DMSO solutions at room temperature. For the methyl-and methoxy-substituted TBT derivatives, the fluorescence emission peak were slightly red shifted relative to that of unsubstituted TBT (Δλem = 1–12 nm) whereas, in the case of 6-MeO-TBT-2-COOMe, a rather strong red-shift (Δλem = 73 nm) was attributed to the existence of a “push-pull” electronic interaction of the MeO and COOMe groups. All ΦF values were rather high, varying between 0.11 and 0.35, according to the substituent effect. Fluorescence decays were mono-exponential and τF values were very short, ranging between 0.11 and 0.30 ns for the substituted TBT derivatives until study.