Excited-state dynamics of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate.

The photophysics and excited-state dynamics of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate (EAADCy) in solvents of varying polarity and viscosity have been studied using femtosecond transient absorption spectroscopy. Global analysis of the time-resolved spectra revealed three processes occurring in an optically excited molecule. The sequence of reactions begins with a transition from an initially excited Franck-Condon state to the nonrelaxed intramolecular charge transfer (ICT(NR)) state which is associated with a partial electron transfer. This process is followed by an additional relaxation to a more relaxed intramolecular charge transfer (ICT(R)) state with stronger charge transfer character and flattened geometry. The lifetime of the flattened charge transfer form (ICT(R)) shortens from 200 to 300 ps in medium polar solvents down to 10 ps in strongly polar solvents. On the other hand, increase of viscosity by 1 order of magnitude leads to deceleration of processes involving twist of the donor and acceptor moieties by a factor of approximately 2.5. Observation of long-lived fluorescence of EAADCy in medium polar solvent suggests that charge transfer is possible only from a hot Franck-Condon state, but not from a relaxed locally excited state which exhibits short-wavelength fluorescence on a nanosecond time scale.