Quantum mechanics/molecular mechanics studies on mechanistic photophysics of cytosine aza-analogues: 2,4-diamino-1,3,5-triazine and 2-amino-1,3,5-triazine in aqueous solution

Abstract

The excited-state properties and photophysics of cytosine aza-analogues, i.e., 2,4-diamino-1,3,5-triazine (2,4-DT) and 2-amino-1,3,5-triazine (2-AT) in solution have been systematically explored using the QM(MS-CASPT2//CASSCF)/MM approach. The excited-state nonradiative relaxation mechanisms for the initially photoexcited S₁(ππ*) state decay back to the S₀ state are proposed in terms of the present computed minima, surface crossings (conical intersections and singlet–triplet crossings), and excited-state decay paths in the S₁, S₂, T₁, T₂, and S₀ states. Upon photoexcitation to the bright S₁(ππ*) state, 2,4-DT quickly relaxes to its S₁ minimum and then overcomes a small energy barrier of 5.1 kcal mol⁻¹ to approach a S₁/S₀ conical intersection, where the S₁ system hops to the S₀ state through S₁ → S₀ internal conversion (IC). In addition, at the S₁ minimum, the system could partially undergo intersystem crossing (ISC) to the T₁ state, followed by further ISC to the S₀ state via the T₁/S₀ crossing point. In the T₁ state, an energy barrier of 7.9 kcal mol⁻¹ will trap 2,4-DT for a while. In parallel, for 2-AT, the system first relaxes to the S₁ minimum and then S₁ → S₀ IC or S₁ → T₁ → S₀ ISCs take place to the S₀ state by surmounting a large barrier of 15.3 kcal mol⁻¹ or 11.9 kcal mol⁻¹, respectively, which heavily suppress electronic transition to the S₀ state. Different from 2,4-DT, upon photoexcitation in the Franck–Condon region, 2-AT can quickly evolve in an essentially barrierless manner to nearby S₂/S₁ conical intersection, where the S₂ and T₁ states can be populated. Once it hops to the S₂ state, the system will overcome a relatively small barrier (6.6 kcal mol⁻¹vs. 15.3 kcal mol⁻¹) through IC to the S₀ state. Similarly, an energy barrier of 11.9 kcal mol⁻¹ heavily suppresses the T₁ state transformation to the S₀ state. The present work manifests that the amination/deamination of the triazine rings can affect some degree of different vertical and adiabatic excitation energies and nonradiative decay pathways in solution. It not only rationalizes excited-state decay dynamics of 2,4-DT and 2-AT in aqueous solution but could also provide insights into the understanding of the photophysics of aza-nucleobases.