Solvent assisted excited-state deactivation pathways in isolated 2,7-diazaindole-S1-3 (S = Water and Ammonia) complexes

The role of solvent molecules in the deactivation of photo-excited 2,7-diazaindole (DAI) – (H2O)1-3 and DAI – (NH3)1-3 complexes were computationally investigated. An excited-state proton transfer (ESPT) path from the solvent to the DAI molecule was followed using the TD-DFT-D4 (B3LYP) level of theory. The computed potential energy profile of ESPT process has shown intersection between ππ* and nπ* states facilitated via relative stabilization of the nπ* state with decreasing N(7)-Hb bond length. The ESPT process, starting from the DAI-Sn (ππ*) state, crosses through a barrier ranging from 27 to 36 kJmol−1 for water complexes and 26–30 kJmol−1 for ammonia complexes. The energy of the excited state was rapidly decreased with a shorter N(7)-Hb bond length. Subsequently, a significant trend of finding a second intersection between the ground and the excited state was observed for all the complexes. The results firmly suggested a significant deactivation channel of excited azaindole derivatives. In the present system, two competing channels, ESPT and ESHT, were found to be energetically accessible. The energy barriers associated with the ESPT barriers for DAI-(H2O)1-3 complexes are similar to the ESHT barrier, depicting equal dominance of both processes. The increased basicity of the N(7) atom in the excited state resulted a facile ESPT process from the water to N(7) of the DAI molecule. However, DAI-(NH3)1-3 complexes show clear preference for ESHT over ESPT process owing to its higher gas-phase pKa value making it a poor proton donor. The above systems can be used as a model to computationally and experimentally investigate the competing radiative and deactivation pathways of photo-excited solvated complexes of N-H-bearing bio-relevant molecules via proton and hydrogen transfer reactions. © 2022 Elsevier B.V