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Ultrafast Dynamics of the Transoid-cis Isomer Formed in Photochromic Reaction from 3H-Naphthopyran.
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-06-08 , DOI: 10.1002/cphc.202000294
Sabina Brazevic 1 , Mikołaj Baranowski 1 , Marek Sikorski 2 , Michał F Rode 3 , Gotard Burdziński 1
Affiliation  

Recent efforts in designing new 3H‐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 TCTT isomerization process. Transient absorption spectroscopy reveals a very short lifetime of the singlet excited TC (≈0.8 ps) and its deactivation channels as S1→S0 internal conversion (major), intersystem crossing S1→T1, pyran ring formation, photoenolization and TCTT isomerization. Computations support the S1→S0 and T1→S0 channels as responsible for photostabilization of the TC form.

中文翻译:

从3H-萘并吡喃光致变色反应中形成的反式-顺式异构体的超快动力学。

最近设计新的3 H-萘并吡喃衍生物的努力集中在有效的着色过程上,而彩色的反式-顺式 TC异构体的褪色时间短。避免TC在光反应中导致Transoid- trans TT异构体的发生是合乎需要的。TT的长寿命会阻碍快速应用,例如动态全息材料和分子致动器,残余颜色是光致变色镜片的严重问题之一。在这里,我们表征了TC激发态失活与不需要的TCTT竞争的光物理和光化学通道异构化过程。瞬态吸收光谱显示单线激发TC的寿命很短(≈0.8ps),其钝化通道为S 1 →S 0内部转化(主要),体系间交叉S 1 →T 1,吡喃环形成,光致脱色和TCTT异构化。计算支持S 1 →S 0和T 1 →S 0通道,它们负责TC形式的光稳定化。
更新日期:2020-06-08
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