UV-Vis, Raman spectroscopic and density functional theoretical studies on microsolvation 1, 2, 4-triazole-3-thione...

Photophysical and photochemical reactions of microsolvation clusters are attracting an increasing attention due to their wide applications in materials science and biology. In this paper, 1, 2, 4-triazole-3-thione (3TT) is investigated in solid, protic, and aprotic solvents using FT-Raman, resonance Raman and electronic absorption spectroscopic experiments. The structures of microsolvation clusters in solvents were confirmed by 488 nm Raman spectroscopy combining with density functional theory (DFT) calculation. Steady-state absorption and resonance Raman spectra of 3TT in different environments indicate that the intermolecular hydrogen bonding may reveal important insights in the photophysical and photochemical process. With the aid of DFT and time-dependent density functional theory (TDDFT) calculations, we assigned the observed Raman spectra to the microsolvation clusters in acetonitrile, water and methanol, and carried out preliminary investigations on spectrum shifts of UV and Raman spectra due to the hydrogen bonding with the solvent molecules. The intermolecular >NH···O and >=S···H hydrogen bonding interactions, which are the key constituents of stable thione structure of 3TT, revealed the obvious spectrum shifts of 3TT, including Raman and absorption shifts in CH₃CN, CH₃OH and H₂O. The hydrogen bond sites were further confirmed to be located on the functional group SCNH of 3TT with CH₃CN, H₂O and CH₃OH.