Perfluoroalkylated anthracene endoperoxide: Synthesis, characterization, crystal structure analysis, and computational insights
Perfluoroalkylated anthracene endoperoxide: Synthesis, characterization, crystal structure analysis, and computational insights
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DOI：
10.1016/j.jfluchem.2020.109548
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发表时间：
2020-07
影响因子：
1.9
通讯作者：
Anjaneyulu Putta;Andrew G Sykes;Haoran Sun
中科院分区：
文献类型：
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作者：
Anjaneyulu Putta;Andrew G Sykes;Haoran Sun
芳香内氧化物是产生单态氧的重要中间物种，是光动力疗法应用的关键。获得微调内过氧化稳定性和氧-氧键激活程度的见解对化学和医药界具有重要的基础和实际意义。本文报道了9，10-双全氟辛基-菲在室温下在光照和空气中几乎被定量地转化为9，10-双全氟辛基-蒽内过氧物(化合物1)。1H核磁共振谱和X-射线晶体结构表明，所得化合物1在室温下是稳定的，不会进一步分解。晶体结构分析表明，化合物1由F···O分子内相互作用以及F···F、F···H和F···C分子间相互作用稳定。密度泛函理论计算进一步表明，由Oone-Bondo、Cone Bondo键距变化所反映的蒽内过氧物中氧-氧键的活化程度可能不完全取决于9，10-位取代基的电子效应。这种不确定性需要在实验和计算上进行进一步的研究。
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 9,10-bisperfluorooctyl-anthracene, upon exposing to light and air, is almost quantitatively converted to 9,10-bisperfluorooctyl-anthracene endoperoxide (compound1) at room temperature.1H NMR spectra and the X-ray crystal structure revealed that the resulting compound1is stable at room temperature without further decomposition. The crystal structure analysis showed that the compound1is 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 Osingle bondO, Csingle bondO bond distances, may not solely depend on the electronic effect of substituents at the 9,10- positions. This uncertainty warrants further investigation both experimentally and computationally.