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The Watson-Crick A·T and G·C base pairs are not only electronically complementary, but also photochemically complementary. Upon UV irradiation, DNA base pairs undergo efficient excited-state deactivation through electron driven proton transfer (EDPT), also known as proton-coupled electron transfer (PCET), at a rate too fast for other reactions to take place. Why this process occurs so efficiently is typically reasoned based on the oxidation and reduction potentials of the bases in their electronic ground states. Here, we show that the occurrence of EDPT can be traced to a reversal in the aromatic/antiaromatic character of the base upon photoexcitation. The Watson-Crick A·T and G·C base pairs are aromatic in the ground state, but the purines become highly antiaromatic and reactive in the first 1 ππ* state, and transferring an electron and a proton to the pyrimidine relieves this excited-state antiaromaticity. Even though proton transfer proceeds along the coordinate of breaking a N-H σ-bond, the chromophore is the π-system of the base, and EDPT is driven by the strive to alleviate antiaromaticity in the π-system of the photoexcited base. The presence and absence of alternative excited-state EDPT routes in base pairs also can be explained by sudden changes in their aromatic and antiaromatic character upon photoexcitation.

Electron-driven proton transfer relieves excited-state antiaromaticity in photoexcited DNA base pairs