Solvatochromic investigation of highly fluorescent 2-aminobithiophene derivatives

Abstract

The solvatochromic and electrochemical properties of electronic push–pull 2-aminobithiophenes consisting of an aldehyde and nitro withdrawing groups were examined. With the use of an integrating sphere, the absolute quantum yields of the bithiophenes were measured. They were found to be highly fluorescent (Φ_fl > 70%), provided the nitro group was not located in the 4′-position. High fluorescence yields were observed regardless of solvent, except for alcohols, notably methanol and ethanol. Cryofluorescence was used to probe the bithiophene temperature dependent excited state deactivation modes. The singlet excited state deactivation mode other than fluorescence was found to be internal conversion involving rotation around the thiophene–thiophene bond. Deactivation by intersystem crossing to the triplet state occurred in ca. 40% only for the unsubstituted 2-aminobithiophene. In contrast, the fluorescence was quenched by photoinduced intramolecular electron transfer when the nitro group was located in the 4′-position of the bithiophene. Both the absorbance and fluorescence of the bithiophenes were found to be solvatochromic with more pronounced solvent dependent shifts being observed with the fluorescence. In fact, both the fluorescence and Stokes shifts were linearly dependent on the E_T(30) solvent parameter. Deviations from the linear trend of the Stokes shift with E_T(30) were observed in ethanol and methanol as a result of intermolecular hydrogen abstraction from the solvent and by the excited nitro group. The oxidation potential of the bithiophenes was also highly dependent on the type and number of the electron withdrawing substituents, with values ranging between 0.8 and 1.2 V vs. SCE.