T₁ Population as the Driver of Excited-State Proton-Transfer in 2-Thiopyridone.

ABSTRACT: Excited-state proton transfer (ESPT) is a fundamental process in biomolecular photochemistry, but its underlying mediators often evade direct observation. We identify a distinct pathway for ESPT in aqueous 2-thiopyridone, by employing transient N 1s X-ray absorption spectroscopy and multi-configurational spectrum simulations. Photoexcitations to the singlet S₂ and S₄ states both relax promptly through intersystem crossing to the triplet T₁ state. The T₁ state, through its rapid population and near nanosecond lifetime, mediates nitrogen site deprotonation by ESPT in a secondary intersystem crossing to the S₀ potential energy surface. This conclusively establishes a dominant ESPT pathway for the system in aqueous solution, which is also

SUBMITTER: Eckert S 

PROVIDER: S-EPMC6470867 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature