An nπ* gated decay mediates excited-state lifetimes of isolated azaindoles

Aiming to serve as a guide to understand the relaxation mechanisms of more complex aza-aromatic compounds, such as purine bases, we have studied the non-radiative channels of a set of azaindole structural isomers: 4-, 5-, 6- and 7-azaindole (AI). The relaxation of the isolated molecules, after excitation at the low energy portion of their spectra, has been tracked by femtosecond time-resolved ionization, and the decay paths have been obtained with MS-CASPT2//TD-DFT calculations. Although the ultrashort measured lifetimes for5-and6-AIare in contrast to the long-living excited state found in7-AI, the calculations describe a common relaxation pathway. Along it, the initially excited pi pi* states decay to the ground state through a conical intersection accessed through an n pi* state that functions as a gate state. The work reveals that the position of the nitrogen atoms in the purine ring determines the barrier to access the gate state and therefore, the rate of the non-radiative relaxation.