The possible role of radical species in the formation of the long-lived triplet states observed for 2-thiocytosine upon UV irradiation was theoretically investigated. It is predicted that the radical fragments arising from the homolytic rupture of the NH group of the thiobase can be yielded upon ultraviolet-A radiation. Recombination of the radicals through the most favorable singlet channel yields the lowest-lying tautomer of the 2-thiocytosine (the amino-thiol form) through a barrierless pathway. The rebounding of the radical fragments along the triplet channels that emerge from the attack of the hydrogen to the nitrogen atoms next to the C-S bond leads to stable structures for the amino-thion-N1H and amino-thion-N3H tautomers. These results allow for the rationalization of the near-unity triplet yields observed when this pure light-atom organic molecule is exposed to UV irradiation, without invoking intersystem crossings between the electronic states of different spin-multiplicities. A similar study for cytosine showed that the energy required to induce the homolytic breaking of the N-H bond of the nucleobase is not attainable under UVA radiation. This result is consistent with the experimental fact that no triplet states are observed when this molecule is exposed to that light.
© 2024 The Authors. Published by American Chemical Society.