Unexpected longer T1 lifetime of 6-sulfur guanine than 6-selenium guanine: the solvent effect of hydrogen bonds to brake the triplet decay

Abstract

The decay of the T₁ state to the ground state is an essential property of photosensitizers because it decides the lifetime of excited states and, thus, the time window for sensitization. The sulfur/selenium substitution of carbonyl groups can red-shift absorption spectra and enhance the triplet yield because of the large spin–orbit coupling, modifying nucleobases to potential photosensitizers for various applications. However, replacing sulfur with selenium will also cause a much shorter T₁ lifetime. Experimental studies found that the triplet decay rate of 6-seleno guanine (6SeGua) is 835 times faster than that of 6-thio guanine (6tGua) in aqueous solution. In this work, we reveal the mechanism of the T₁ decay difference between 6SeGua and 6tGua by computing the activation energy and spin–orbit coupling for rate calculation. The solvent effect of water is treated with explicit microsolvation and implicit solvent models. We find that the hydrogen bond between the sulfur atom of 6tGua and the water molecule can brake the triplet decay, which is weaker in 6SeGua. This difference is crucial to explain the relatively long T₁ lifetime of 6tGua in an aqueous solution. This insight emphasizes the role of solvents in modulating the excited state dynamics and the efficiency of photosensitizers, particularly in aqueous environments.