Ultrafast Dynamics of the Transoid‐cis Isomer Formed in Photochromic Reaction from 3H‐Naphthopyran

Abstract Recent efforts in designing new 3 H ‐naphthopyran derivatives have been focused on efficient coloration process with a short fading time of the colored transoid‐ cis TC isomer. It is desirable to avoid photoisomerization of TC leading to transoid‐ trans TT isomers in the photoreaction. Long lifetime of TT can hamper fast applications such as dynamic holographic materials and molecular actuators, the residual color is one of the serious issues for photochromic lenses. Herein we characterize the photophysical and photochemical channels of TC excited state deactivation competing with the unwanted TC → TT isomerization process. Transient absorption spectroscopy reveals a very short lifetime of the singlet excited TC (≈0.8 ps) and its deactivation channels as S 1 →S 0 internal conversion (major), intersystem crossing S 1 →T 1 , pyran ring formation, photoenolization and TC → TT isomerization. Computations support the S 1 →S 0 and T 1 →S 0 channels as responsible for photostabilization of the TC form.