Remote electron and energy transfer sensitized photoisomerization of encapsulated stilbenes
Remote electron and energy transfer sensitized photoisomerization of encapsulated stilbenes
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DOI：
10.1039/d0pp00115e
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发表时间：
2020-06
影响因子：
3.1
通讯作者：
Ramkumar Varadharajan;A. Raj;V. Ramamurthy
中科院分区：
文献类型：
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作者：
Ramkumar Varadharajan;A. Raj;V. Ramamurthy
激发的态化学和分子的物理学除了固有的电子和空间特征之外，还取决于它们的直接微环境。这项研究探讨了有机胶囊的影响，比反应物分子本身稍大，对封装分子的激发态化学。此处介绍的结果表明，实际上，即使没有直接的物理相互作用，也可以从外部进行操纵，实际上，受限值的分子也可以操纵。提出了通过电子和能量传递过程引发的限制分子和外部出现的自由分子之间通信的示例。检查了通过阳离子敏化剂诱导的能量和电子转移诱导的八酸的几何异构化。当兴奋的外部敏化剂兴奋时，异构化发生的事实表明，反应物和敏化剂正在跨胶囊的分子壁进行通信。能够远程激活限制分子的能力为通过长距离能量和电子传递过程产生的狭窄自由基离子和三胞胎激发分子的反应提供了新的机会。
Excited state chemistry and physics of molecules, in addition to their inherent electronic and steric features, depend on their immediate microenvironments. This study explores the influence of an organic capsule, slightly larger than the reactant molecule itself, on the excited state chemistry of the encapsulated molecule. Results presented here show that the confined molecule, in fact, is not isolated and can be manipulated from outside even without direct physical interaction. Examples where communication between a confined molecule and a free molecule present outside is brought about through electronic and energy transfer processes are presented. Geometric isomerization of octa acid encapsulated stilbenes induced by energy and electron transfer by cationic sensitizers that attach themselves to the anionic capsule is examined. The fact that isomerization occurs when the sensitizer present outside is excited illustrates that the reactant and sensitizer are communicating across the molecular wall of the capsule. Ability to remotely activate a confined molecule opens up new opportunities to bring about reactions of confined radical ions and triplet excited molecules generated via long distance energy and electron transfer processes.