Resonance Raman spectroscopic and density functional theoretical study on microsolvated 2-Thiocytosine clusters with polar solvents

Abstract Microsolvation effects on the excited state deactivation dynamics of 2-thiocytosine (2tC) were studied in hydrogen-bonded 2tC clusters with protic solvents using resonance Raman, FT-IR, FT-Raman, UV–vis spectroscopy combining with density functional theoretical calculation. Two protic solvents, water (H2O) and methanol (MeOH), and one aprotic solvent, acetonitrile (MeCN), were used to investigate the 2tC(H2O)1–5, 2tC(MeOH)1–5, and 2tC(MeCN)1–3 microsolvated clusters. In CH3OH and H2O solvents, most of the Raman shifts were due to the vibration modes of 2tC(solvent)n (solvent = H2O, CH3OH; n = 1–4) clusters via intermolecular NH⋯O hydrogen bonds (HB). The intermolecular >NH⋯O hydrogen bond interactions, which are the key constituents of stable thione structure of 2tC, revealed the spectra difference of 2tC in CH3CN, CH3OH and H2O. With the aid of electronic structural and vibration frequency calculations, the observed Raman spectra were assigned to the low energy isomers of 2tC(solvent)2 (solvent = H2O, CH3OH) clusters in water and methanol and 2tC(CH3CN) in acetonitrile solvents. 2tC(solvent)2 clusters in water and methanol may prohibit or promote excited state proton transfer reaction from sulfur atom to neighbor nitrogen atom due to the hydrogen bonding chain between 2tC and protic solvent molecules. Our experimental and theoretical studies confirmed that the hydrogen bond sites were located on the specified functional group S CNH of 2tC with solvent molecules.