Experimental and Computational Analysis of Para-Hydroxy Methylcinnamate following Photoexcitation.
Experimental and Computational Analysis of Para-Hydroxy Methylcinnamate following Photoexcitation.
复制标题
光激发对羟基甲基肉桂酸酯的实验与计算分析。
DOI：
10.3390/molecules26247621
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发表时间：
2021-12-15
期刊：
影响因子：
--
通讯作者：
Stavros VG
中科院分区：
文献类型：
--
作者：
Dalton J;Richings GW;Woolley JM;Abiola TT;Habershon S;Stavros VG
对羟基甲基肉桂酸是肉桂酸家族分子的一部分。实验和计算研究表明，光激发到S1（π *）态后，非辐射衰变路径相互矛盾。一种非辐射衰变途径涉及由光学暗单重态介导的系统间交叉，而另一种涉及直接系统间交叉到三重态。此外，无论衰变机制如何，初始填充态S1（ππ*）的寿命仍有待精确测量。在这项研究中，我们使用时间分辨离子产率和光电子能谱来精确测定对羟基甲基肉桂酸的s顺式构象的S1（ππ*）寿命，并结合时间依赖的密度泛函理论来确定主要的非辐射衰变途径。我们发现s-顺式对羟基甲基肉桂酸的S1（π *）态寿命为~ 2.5皮秒，主要的非辐射衰变路径遵循[1ππ*→1nπ*→3ππ*→S0]途径。这些结果也与先前对结构相似的分子（如对香豆酸和甲基肉桂酸）的光动力学研究相一致。
Para-hydroxy methylcinnamate is part of the cinnamate family of molecules. Experimental and computational studies have suggested conflicting non-radiative decay routes after photoexcitation to its S1(ππ*) state. One non-radiative decay route involves intersystem crossing mediated by an optically dark singlet state, whilst the other involves direct intersystem crossing to a triplet state. Furthermore, irrespective of the decay mechanism, the lifetime of the initially populated S1(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S1(ππ*) lifetime for the s-cis conformer of para-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S1(ππ*) state lifetime of s-cis para-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [1ππ*→1nπ*→3ππ*→S0] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as para-coumaric acid and methylcinnamate.
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