Femtosecond fluorescence and absorption dynamics of an azobenzene with a strong push-pull substitution

The ultrafast photoisomerization of a push-pull substituted azobenzene (4-nitro-4'-(dimethylamino)azobenzene, NA) is studied by means of femtosecond fluorescence and absorption spectroscopy. The fluorescence dynamics is biphasic. The initial fluorescence with a narrow and intense spectrum decays in similar to100 fs. This decay is accompanied by the rise of broad red-shifted and much weaker emission. The same time constants recur in the transient absorption spectra which hold additional information on the ground-state dynamics. The ground state recovers in 0.8 ps, demonstrating that only the longer time constant is associated with an internal conversion process. Small spectral changes occurring thereafter (similar to5 ps) point to vibrational cooling in the ground state. The results are analyzed in comparison with the behavior of the parent compound azobenzene. Though the push-pull substitution of azobenzene strongly alters the character of its excited states, the photodynamics are surprisingly robust with respect to that substitution.