Dual fluorescent polyaniline model compounds: steric and temperature effects on excited state charge separation

Low temperature dual fluorescence of several derivatives of 4-aminodiphenylamine is investigated quantitatively. A strong thermochromic and solvatochromic redshift is indicative of the high dipole moment of the CT state emitting at long wavelength. The combination of steady state and time-resolved data allowed the calculation of the excited-state equilibrium. The absence of CT-risetimes in diethyl ether and their presence in butyronitrile points to the complication by additional around state conformational equilibria. Both ground and excited state equilibria depend on solvent polarity and temperature. High solvent polarity favours one of the ground state conformers.