UV-Vis, Fluorescence, and Resonance Raman Spectroscopic and Density Functional Theoretical Studies on 3-Amino-1,2,4-triazole: Microsolvation and Solvent-Dependent Nonadiabatic Excited State Decay in Solution.

The microsolvation and photophysics of 3-amino-1,2,4-triazole (3AT) after excitation to the light-absorbing S2(nπ*) state were studied by using resonance Raman spectroscopy and single component artificial force-induced reaction (SC-AFIR) in a global reaction route mapping (GRRM) strategy. The vibrational spectra were assigned on the basis of experimental data and density functional theory (DFT) calculations. The resonance Raman spectra of 3AT were measured to probe the excited state structural dynamics in the Franck-Condon region. The conformations of 3AT(CH3CN)1, 3AT(CH3OH)2, and 3AT(H2O)2 clusters were determined by combining vibrational spectrum experiments and B3LYP/6-311++G(d,p) computations. DFT calculations were carried out to obtain the minimal excitation energies of the lower-lying singlet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of 3AT were dominated by the N-N stretching coordinates. An excited state decay mechanism is proposed: 3AT is initially excited to the S2(nπ*) state, then the conical intersection (CI) of the S2(nπ*)/S1(ππ*) potential energy surfaces is crossed, and 3AT then decays to the lower solvent-dependent excited state S1(ππ*). It subsequently returns to the S0 state, accompanied by a large Stokes fluorescence shift, which was interpreted as the stabilized S1(ππ*) excited state bonding to several water molecules via intermolecular hydrogen bonding.

Absorption, fluorescence, Raman spectroscopic and density functional theoretical studies on the singlet and triplet excited state decay of 3-amino-5-mercapto-1,2,4-triazole.

The excited state decay process of N-heterocyclic compounds is attracting increasing attention due to their fundamental applications in pharmaceutical and biological sciences. In this study, 3-amino-5-mercapto-1,2,4-triazole (AMT) was investigated in solid, protic, and aprotic solvents using vibrational and electronic spectroscopies combined with density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The steady absorption and resonance Raman spectra indicated that the AMT structure was quite sensitive to the polarity and proton of the solvent, and the pH environments. The intermolecular hydrogen bonding may contribute significantly to the decay channels of the singlet excited S2(ππ*) state process. Moreover, ns-transient absorption spectroscopy detected the short-time triplet species with ∼200 ns lifetime in solvents. The DFT and TDDFT calculations interpreted the photophysical and photochemical process from the excited S2(ππ*) state, including the singlet and triplet decay mechanisms.