thiouracil and 2-thiothymine

The ultrafast internal conversion and intersystem crossing dynamics of 2-thiouracil (2TU) and 2-thiothymine (2TT) are studied using time-resolved photoelectron spectroscopy to investigate the effect of methylation on the deactivation mechanism. Like other thiobases, the triplet manifold is populated with high quantum yields via the lowest singlet excited state, which is dark in absorption. This study focuses on the lowest triplet state and the role of two minima, with sulfur-out-of-plane and slightly boat-like geometries, in the intersystem crossing dynamics back to the ground state.

Topics: Methylation; Photoelectron Spectroscopy; Thiouracil; Thymine

Femtosecond broadband transient absorption experiments are reported for 2-thiothymine and 2-thiouracil in aqueous buffer solution and in acetonitrile. It is shown that the S1(nπ*) state acts as a doorway state in the ultrafast and efficient population of the T1(ππ*) state upon 316 nm excitation. A sequential kinetic model is presented to explain the excited-state dynamics in 2-thiothymine and 2-thiouracil upon UVA excitation: S2(ππ*) → S1(nπ*) → T1(ππ*). The experimental results are also used to scrutinize the excited-state relaxation pathways recently predicted for 2-thiouracil at the CASPT2//CASSCF level of theory [G. Cui and W. Fang, J. Chem. Phys. 138, 044315 (2013)]. The efficient population of the T1(ππ*) state for both 2-thiothymine and 2-thiouracil in a few hundreds of femtoseconds lends further support to the emerging idea that thiobase derivatives exhibit photo-toxic properties that can be effectively harnessed in photo-chemotherapeutic applications.

Topics: Acetonitriles; Buffers; Electrons; Kinetics; Quantum Theory; Spectrophotometry, Ultraviolet; Thiouracil; Thymine

The aim of the present work is to determine the influence of C5 substitution on the photophysical properties of 2-thiopyrimidines (2-TPyr). For this purpose, 2-thiouracil, 5-t-butyl-2-thiouracil and 2-thiothymine (TU, BTU and TT, respectively) have been selected as target thionucleobases for the experimental studies and, in parallel, for DFT theoretical calculations. The UV spectra displayed by TU, BTU and TT in EtOH were very similar to each other. They showed a maximum around 275 nm and a shoulder at ca. 290 nm. The three 2-TPyr exhibited a strong phosphorescence emission; from the recorded spectra, triplet excited state energies of ca. 307, 304 and 294 kJ mol(-1) were determined for TU, BTU and TT, respectively. Laser excitation at 308 nm gave rise to a broad transient absorption band from 500 nm to 700 nm, which was in principle assigned to triplet-triplet absorption. This assignment was confirmed by energy transfer experiments using biphenyl (ET = 274 kJ mol(-1)) as an acceptor. The triplet lifetimes were 70 ns, 1.1 μs and 2.3 μs, for TU, BTU and TT, respectively. The obtained photophysical data, both in phosphorescence and transient absorption measurements, point to significantly different properties of the TT triplet excited state in spite of the structural similarities. Theoretical calculations at the B3LYP/aug-cc-pVDZ/PCM level agree well with the experimental range of excited state energies and support the ππ* nature of the lowest triplet states.

Topics: Models, Molecular; Molecular Conformation; Quantum Theory; Spectrophotometry, Ultraviolet; Thiouracil; Thymine