Photochemistry with Plane-Polarized Light: Controlling Photochemical Reactivity via Spatially Selective Excitation
Photochemistry with Plane-Polarized Light: Controlling Photochemical Reactivity via Spatially Selective Excitation
复制标题
平面偏振光的光化学：通过空间选择性激发控制光化学反应
DOI：
10.1021/acs.jpclett.0c02473
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发表时间：
2020-10-15
影响因子：
5.7
通讯作者：
Nesterov, Evgueni E.
中科院分区：
文献类型：
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作者：
Anokhin, Maksim, V;Nesterov, Evgueni E.
光化学反应本质上很难控制，因为它们涉及高能激发态物种。在这里，我们报道了一种利用特定电子跃迁的空间选择性激发来控制光化学反应的新方法。这可以使用在向列相液晶(LC)介质中均匀排列的光反应化合物的平面偏振光的光化学照射来实现。在选择了环丙烯酮光脱羰反应作为概念验证反应后，我们证明了可以通过改变入射光偏振面与LC指向矢之间的角度来控制该反应。我们发现两个特定的部分禁止的电子跃迁是造成这种光化学反应的主要原因。我们设想，这种简单通用的方法可以用于各种光化学过程的基本细节的实验研究，并有助于提高光化学转化的选择性。
Photochemical reactions are intrinsically difficult to control because they involve high-energy excited-state species. Herein we report a novel approach toward controlling photochemical reactions via using the spatially selective excitation of specific electronic transitions. This can be performed using photochemical irradiation with the plane-polarized light of a photoreactive compound uniformly aligned in a nematic liquid-crystalline (LC) medium. Having chosen cyclopropenone photodecarbonylation as a proof-of-concept reaction, we demonstrated that it could be controlled via changing an angle between the incident light polarization plane and the LC director. We showed that two specific partially forbidden electronic transitions were mostly responsible for this photochemical reaction. We envision that this simple general method can be useful in experimental studies of the fundamental details of various photochemical processes and can help to increase the selectivity of photochemical transformations.