Mechanically interlocked pyrene-based photocatalysts
Mechanically interlocked pyrene-based photocatalysts
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DOI：
10.1038/s41929-022-00799-y
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发表时间：
2022-06-01
期刊：
影响因子：
37.8
通讯作者：
Fraser Stoddart, J.
中科院分区：
文献类型：
--
作者：
Garci, Amine;Weber, Jacob A.;Fraser Stoddart, J.
三重态激发态有机发色团为光催化应用提供了无数的机会。在这里，我们描述了一种芳香族发色团三重激发态的工程方法，其中涉及将芘掺入含吡啶鎓的机械联锁分子（MIM）中。芘的 pi 延伸性质强制[pi center dot center dot center dot pi]堆叠，提供四发色八阳离子均[2]链烷的有效合成。由于混合电荷转移/激基复合物电子态和纳米限域效应的形成，这些MIM产生三重态种群和有效的系间窜越，这导致对三重态的高水平保护并延长了三重态寿命和产量。这些化合物在光氧化中表现出优异的催化活性，硫芥模拟物的有氧氧化证明了这一点。这项研究强调了使用机械键微调现有芳香族发色团的三重态光物理的好处，为开发未开发的基于 MIM 的光敏剂和光催化剂提供了途径。
Triplet excited-state organic chromophores present countless opportunities for applications in photocatalysis. Here we describe an approach to the engineering of the triplet excited states of aromatic chromophores, which involves incorporating pyrene into pyridinium-containing mechanically interlocked molecules (MIMs). The pi-extended nature of the pyrenes enforces [pi center dot center dot center dot pi] stacking, affording an efficient synthesis of tetrachromophoric octacationic homo[2]catenanes. These MIMs generate triplet populations and efficient intersystem crossing on account of the formation of a mixed charge-transfer/exciplex electronic state and a nanoconfinement effect, which leads to a high level of protection of the triplet state and extends the triplet lifetimes and yields. These compounds display excellent catalytic activity in photo-oxidation, as demonstrated by the aerobic oxidation of a sulfur-mustard simulant. This research highlights the benefits of using the mechanical bond to fine-tune the triplet photophysics of existing aromatic chromophores, providing an avenue for the development of unexplored MIM-based photosensitizers and photocatalysts.