Competing Excited-State Hydrogen and Proton-Transfer Processes in 6-Azaindole-S3,4 and 2,6-Diazaindole-S3,4 Clusters (S=H2O, NH3)

Excited state hydrogen (ESHT) and proton (ESPT) transfer reaction pathways in the three and four solvent clusters of 6-azaindole (6AI-S-3,S-4) and 2,6-diazaindole (26DAI-S-3,S-4)(S=H2O, NH3) were computationally investigated to understand the fate of photo-excited biomolecules. The ESHT energy barriers in (H2O)(3) complexes (39.6-41.3 kJmol(-1)) were decreased in (H2O) 4 complexes (23.1-20.2 kJmol(-1)). Lengthening the solvent chain lowered the barrier because of the relaxed transition states geometries with reduced angular strains. Replacing the water molecule with ammonia drastically decreased the energy barriers to 21.4-21.3 kJmol(-1) in (NH3)(3) complexes and 8.1-9.5 kJ mol(-1) in (NH3)(4) complexes. The transition states were identified as Ha atom attached to the first solvent molecule. The formation of stronger hydrogen bonds in (NH3)(3,4) complexes resulted in facile ESHT reaction than that in the (H2O)(3,4) complexes. The ESPT energy barriers in 6AI-S-3,S-4 and 26DAI-S-3,S-4 were found to range between 40-73 kJmol(-1). The above values were significantly higher than that of the ESHT processes and hence are considered as a minor channel in the process. The effect of N(2) insertion was explored for the very first time in the isolated solvent clusters using local vibrational mode analysis. In DAI-S-4, the higher K-a(H-a center dot center dot center dot S-a) values depicted the increased photoacidity of the N(1)-H-a group which may facilitate the hydrogen transfer reaction. However, the increased N(6)center dot center dot center dot H-b bond length elevated the reaction barriers. Therefore, in the ESHT reaction channel, the co-existence of two competing factors led to a marginal/no change in the overall energy barriers due to the N(2) insertion. In the ESPT reaction pathway, the energy barriers showed notable increase upon N(2) insertion because of the increased N(6)center dot center dot center dot H-b bond length.