Excited-State Intramolecular Proton Transfer toward Conical Intersections in Indigo, Epindolidione, and Indirubin.

Indigo exhibits a high degree of photostability, experimentally supported by observations such as quenching of fluorescence and an exceptionally short excited-state lifetime. Epindolidione, a structural isomer of indigo, is highly fluorescent in contrast to indigo, while indirubin, another structural isomer, exhibits weak fluorescence similar to that of indigo. To elucidate the origin of the difference in photophysical and photochemical behavior, potential energy profiles of the excited-state intramolecular proton transfer in indigo, epindolidione, and indirubin are computationally studied by quantum chemical calculations using the TDDFT and extended MS-CASPT2 (XMS-CASPT2) methods. As a result, it is found that indigo and indirubin exhibit little energy barrier for the single proton transfer (SPT) in the S₁(ππ*) state from the diketo to keto-enol form and low energy of the S₁/S₀ conical intersection (CI) in the latter form with a planar molecular structure. Epindolidione, on the other hand, exhibits much higher barriers for SPT and access to CI. These results suggest that the excited-state SPT and subsequent nonradiative deactivation via CI are more likely to occur in indigo and indirubin than in epindolidione, which is consistent with the experimental observations described above. For indigo and epindolidione, the deactivation channels via the second SPT from the keto-enol to dienol form are also compared.