Excited-State Aromatization Drives Nonequilibrium Planarization Dynamics.

Excited-state aromaticity is one of the most widely applied concepts in the field of chemistry, often used as a rational guideline for predicting conformational changes of cyclic π-conjugated systems induced by photoexcitation. Yet, the details of the relationship between the corresponding photoinduced electronic and structural dynamics have remained unclear. In this work, we applied femtosecond transient absorption and time-resolved time-domain Raman spectroscopies to track the nonequilibrium planarization dynamics of a cyclooctatetraene (COT) derivative associated with the excited-state aromaticity.