Synthesis and Characterization of Photosensitive Ionic Liquid Surfactant 4-Butylazobenzene-4′-(Oxyethyl)Methylimidazolium with Br− and BF4− Counterions

The photo-responsive ionic liquid surfactants 4-Butylazobenzene-4′-(oxyethyl)methylimidazolium with Br− (AZMIMBr) and BF4− (AZMIMBF4) counterions were synthesized, and their structures were characterized by means of 1H NMR. Their properties for pre- or post-UV irradiation were investigated by employing tensiometry, electrical conductance, thermal gravimetry-differential scanning calorimetry (TG-DSC) and small-angle X-ray scattering (SAXS). The effect of UV irradiation time on photoisomerization of two surfactants solutions was evaluated, which showed the photoisomerization efficiency decreases with an increase of their concentrations. After UV irradiation, the CMC value of the two surfactants increased, whereas, the surface tensions at CMC (γCMC) and the fraction of counterion binding (β) were approximately the same. SAXS coupled with polarized optical microscopic studies (POM studies) confirmed that the liquid crystal textures of AZMIMBr could be affected by UV-irradiation. The detailed analysis of thermodynamic parameters revealed that the micellizaton of AZMIMBr was entropy-driven, and the micellization of AZMIMBF4 was enthalpy-driven.