School of Pharmaceutical Science and Technology, Tianjin University, 92 Weijin Road, Nankai District, Tianjin, 300072, P. R. China.
Department of Physical and Environmental Sciences, Texas A&M University Corpus Christi, 6300 Ocean Dr, Corpus Christi, Texas, 78412, USA.
Chemistry. 2023 Jun 19;29(34):e202300624. doi: 10.1002/chem.202300624. Epub 2023 May 2.
Polycyclic aromatic endoperoxides are important sources of singlet oxygen ( O ) and their formation from polyacenes is well established. Anthracene carboxyimides are of particular interest as they exhibit excellent antitumor activity and possess unique photochemical properties. However, the photooxygenation of the synthetically versatile anthracene carboxyimide moiety has not been reported due to its competing [4+4] photodimerization reaction. Herein, we describe the reversible photo-oxidation of an anthracene carboxyimide. X-ray crystallographic analysis surprisingly revealed the formation of a racemic mixture of chiral hydroperoxides, rather than the expected endoperoxide. The photoproduct undergoes both photo- and thermolysis to form O . Activation parameters were derived for the thermolysis and the mechanisms of photooxygenation and thermolysis are discussed. The anthracene carboxyimide also showed high selectivity and sensitivity for nitrite anions in acidic aqueous media and possessed stimuli-responsive behaviour.
多环芳烃内过氧化物是单线态氧 ( O ) 的重要来源，它们在多环芳烃中的形成已得到很好的确证。蒽甲酰亚胺因其具有优异的抗肿瘤活性和独特的光化学性质而备受关注。然而，由于其竞争的 [4+4] 光二聚化反应，蒽甲酰亚胺部分的光氧化作用尚未得到报道。在此，我们描述了一种蒽甲酰亚胺的可逆光氧化作用。X 射线晶体学分析出人意料地揭示了手性过氧化物的外消旋混合物的形成，而不是预期的内过氧化物。光产物经历光解和热解，形成 O 。推导了热解的活化参数，并讨论了光氧化和热解的机制。该蒽甲酰亚胺在酸性水介质中对亚硝酸盐阴离子也表现出高选择性和高灵敏度，并具有刺激响应行为。
