Aromatic endoperoxides serve as important intermediate species toward generating singlet state oxygen, which is key to photodynamic therapy applications. Gaining insights for fine-tuning endoperoxide stability and degree of oxygen-oxygen bond activation is of fundamental and practical interest for the chemical and medicinal communities. We report here that 910-bisperfluorooctyl-anthracene, upon exposing to light and air, is almost quantitatively converted to 910-bisperfluorooctyl-anthracene endoperoxide (compound 1) at room temperature. ¹H NMR spectra and the X-ray crystal structure revealed that the resulting compound 1 is stable at room temperature without further decomposition. The crystal structure analysis showed that the compound 1 is stabilized by F···O intramolecular interactions along with F···F, F···H and F···C intermolecular interactions. DFT calculations further indicate that the degree of oxygen-oxygen bond activation in anthracene endoperoxides, reflected as changes of OO, CO bond distances, may not solely depend on the electronic effect of substituents at the 910- positions. This uncertainty warrants further investigation both experimentally and computationally.

芳族过氧化物是产生单重态氧的重要中间物种，这是光动力疗法应用的关键。深入了解内过氧化物稳定性和氧-氧键活化程度的见解对于化学和医学界具有根本和实际意义。我们在此报告910-双全氟辛基-蒽在暴露于光和空气后，在室温下几乎被定量转化为910-双全氟辛基-蒽内过氧化物（化合物1）。¹ H NMR光谱和X射线晶体结构表明，所得化合物1在室温下稳定，没有进一步分解。晶体结构分析表明化合物1通过F··O分子内相互作用以及F··F，F··H和F··C分子间相互作用来稳定。DFT计算进一步表明，蒽内过氧化物中氧-氧键活化的程度反映为O O，C O键距离的变化，可能不仅仅取决于910-位上取代基的电子效应。这种不确定性值得进一步进行实验和计算研究。