T1 Population as the Driver of Excited-State Proton-Transfer in 2-Thiopyridone.,Chemistry - A European Journal

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T1 Population as the Driver of Excited-State Proton-Transfer in 2-Thiopyridone.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-01-08 , DOI: 10.1002/chem.201804166
Sebastian Eckert ₁ , Jesper Norell ₂ , Raphael M Jay ₁ , Mattis Fondell ₃ , Rolf Mitzner ₃ , Michael Odelius ₂ , Alexander Föhlisch _{1,

3}

Affiliation

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 compatible with previous measurements in acetonitrile. Thereby, the hitherto open questions of the pathway for ESPT in the compound, including its possible dependence on excitation wavelength and choice of solvent, are resolved.

中文翻译：

T1人口是2-噻吩并酮中激发态质子转移的驱动因素。

激发态质子转移（ESPT）是生物分子光化学中的基本过程，但其潜在的介体常常逃避直接观察。我们通过采用瞬态N 1s X射线吸收光谱法和多构图谱模拟，确定了2-硫代吡啶酮水溶液中ESPT的独特途径。单线态S2和S4状态的光激发都通过系统间交叉而迅速转变为三线态T1状态。T1状态通过其快速的填充和近十亿分之一秒的寿命，在与SO势能面相交的次要系统间，通过ESPT介导了氮位的去质子化。这最终为水溶液中的系统建立了主要的ESPT途径，这也与先前在乙腈中的测量结果兼容。从而，

更新日期：2019-01-08

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