Excited-State-Selective Ultrafast Relaxation Dynamics and Photoisomerization of trans-4,4'-Azopyridine

Excited-state dynamics of trans-4,4'-azopyridine in ethanol is studied using femtosecond transient absorption with 30 fs temporal resolution. Exciting the system at three different wavelengths, 460 and 290 (275) nm, to access the S₁ nπ* and S₂ ππ* electronic states, respectively, reveals a 195 cm^-1 vibrational coherence, which suggests that the same mode is active in both nπ* and ππ* relaxation channels. Following S₁-excitation, relaxation proceeds via a nonrotational pathway, where a fraction of the nπ* population is trapped in a planar minimum (lifetime, 2.1 ps), while the remaining population travels further to a second shallow minimum (lifetime, 300 fs) prior to decay into the ground state. Population of the S₂ state leads to 30 fs nonrotational relaxation with a concurrent buildup of nπ* population and nearly simultaneous formation of hot ground-state species. An increase in the cis-isomer quantum yield upon ππ* versus nπ* excitation is observed, which is opposite to trans-azobenzene.