Chemically Triggered Release of Singlet Oxygen from Bisphenalenyl Endoperoxides with a Brønsted Acid
Chemically Triggered Release of Singlet Oxygen from Bisphenalenyl Endoperoxides with a Brønsted Acid
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用布伦斯台德酸化学触发双酚基内过氧化物释放单线态氧
DOI：
10.1021/acs.orglett.2c00340
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发表时间：
2022
期刊：
影响因子：
5.2
通讯作者：
Chen, Mark S.
中科院分区：
文献类型：
--
作者：
Imran, Muhammad;Chen, Mark S.
芳香族内过氧物已经成为分子氧(O2)储存和输送的刺激响应材料，但目前它们的应用受到限制，因为它们需要热量来触发O2的释放。在这里，我们提出了第一个不需要外部加热的酸触发单线态氧(1O2)释放的例子，通过用三氟乙酸处理双苯基内过氧物(EPO)。机理研究表明，EPO的二质子化使活化能(ΔEa)降低了71.1kJ·m ol-1，从而使环返向速率提高了10倍。值得注意的是，在室温下甚至还观察到了酸催化的1O2释放。化学捕集实验表明，在酸触发释放过程中存在活性的1O2，这为开发无金属、按需输送1O2的分子材料提供了良好的前景。
Aromatic endoperoxides have emerged as intriguing stimulus-responsive materials for molecular oxygen (O2) storage and delivery but are currently limited in their application because they require heat to trigger O2release. Here we present the first example of acid-triggered singlet oxygen (1O2) release that does not require external heating by treating bisphenalenyl endoperoxides (EPOs) with trifluoroacetic acid. Mechanistic studies reveal that diprotonation of EPOs leads to a >10-fold increase in cycloreversion rates by lowering the energy of activation (ΔEa) by as much as 71.1 kJ mol–1. Remarkably, acid-catalyzed1O2release is even demonstrated at room temperature. Chemical trapping experiments indicate that reactive1O2is present during acid-triggered release, which is promising for the development of these molecular materials for metal-free, on-demand1O2delivery.