Unusual Photoreaction of Triquinacene within Self-Assembled Hosts
Unusual Photoreaction of Triquinacene within Self-Assembled Hosts
复制标题
自组装宿主内三喹苯的不寻常光反应
DOI：
10.1002/asia.201101005
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
M. Fujita
中科院分区：
文献类型：
--
作者：
T. Murase;Y. Nishijima;M. Fujita
三喹二烯是一种凹面三环烃，具有不同的光反应性。在接受电子的分子主体的空腔中，通过客体到主体的电子转移，三喹那烯在外围的烯丙基位置被特异地光氧化为1-羟基三喹二烯。这种不同寻常的反应活性源于主体笼子的极度缺乏电子的三嗪面板配体，这使得笼子能够作为良好的电子受体发挥作用。因此，自组装的配位笼不仅可以作为分子大小的反应容器，还可以作为氧化还原介质的电子功能。溶解的分子氧是光反应不可缺少的，它会立即捕获光生的自由基。
Triquinacene is a concave tricyclic hydrocarbon with diverse photoreactivity. In the cavity of an electron‐accepting molecular host, triquinacene was specifically photooxidized at the peripheral allylic position into an alcohol, 1‐hydroxytriquinacene, via guest‐to‐host electron transfer. The unusual reactivity stems from the extremely electron‐deficient triazine panel ligand of the host cage, which allows the cage to function as a good electron acceptor. Thus, self‐assembled coordination cages can serve not only as molecular‐sized reaction vessels but also function electronically as redox media. Dissolved molecular oxygen is indispensable for the photoreaction and immediately traps a photogenerated radical.