Singlet oxygen (1O2), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry and materials science. Organic conjugated aromatics serving as hosts to capture and release singlet oxygen have been systematically investigated over the last decades. Herein, we present a [6+6] organoplatinum(II) metallacycle by using ~180° dipyridylanthracene donor and ~120° Pt(II) acceptor as the building blocks, which enables the capture and release of singlet oxygen with relatively high photooxygenation and thermolysis rate constants. The photooxygenation of the metallacycle to the corresponding endoperoxide was performed by sensitized irradiation, and the resulting endoperoxide is stable at room temperature and can be stored under ambient condition over months. Upon simple heating the neat endoperoxide under inert atmosphere at 120 oC for 4 h, the resulting endoperoxide can be reconverted to the corresponding parent form and singlet oxygen. The photooxygenation and thermolysis products were characterized by NMR spectroscopy and ESI-TOF-MS analysis. Density functional theory calculations were conducted in order to reveal the frontier molecular orbital interactions and reactivity. This work provides a new material-platform for singlet oxygen related promising applications.

中文翻译：

---

在配位驱动的自组装有机铂 (II) 金属环中捕获和释放单线态氧

单线态氧（1O2）作为一种重要的活性试剂，在光动力疗法（PDT）、合成化学和材料科学中有着广泛的应用。在过去的几十年里，有机共轭芳烃作为捕获和释放单线态氧的主体已经被系统地研究过。在此，我们通过使用~180°二吡啶并蒽供体和~120°Pt(II)受体作为构建单元，提出了一种[6+6]有机铂(II)金属环，它能够捕获和释放具有相对高光氧化作用的单线态氧和热解速率常数。金属环光氧化为相应的内过氧化物是通过敏化辐射进行的，所得内过氧化物在室温下是稳定的，可以在环境条件下储存数月。在惰性气氛下在 120 oC 下简单加热纯内过氧化物 4 小时后，所得内过氧化物可以重新转化为相应的母体形式和单线态氧。通过NMR光谱和ESI-TOF-MS分析表征光氧化和热解产物。进行密度泛函理论计算以揭示前沿分子轨道相互作用和反应性。这项工作为单线态氧相关的有前景的应用提供了一个新的材料平台。进行密度泛函理论计算以揭示前沿分子轨道相互作用和反应性。这项工作为单线态氧相关的有前景的应用提供了一个新的材料平台。进行密度泛函理论计算以揭示前沿分子轨道相互作用和反应性。这项工作为单线态氧相关的有前景的应用提供了一个新的材料平台。