State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology, 100029, Beijing, P. R. China.
Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 100081, Beijing, P. R. China.
Nat Commun. 2019 Feb 15;10(1):767. doi: 10.1038/s41467-019-08434-4.
Radical anions of electron-deficient systems are widely used, but are easily reoxidized upon exposure to air. Therefore, the stabilization of radical anions under ambient conditions is of great significance, but still remains a scientific challenge. Herein, perylenediimide is employed to prepare a crystalline metal-organic framework for stabilizing radical anions without extensive chemical modification. The porous, three-dimensional framework of perylenediimide can trap electron donors such as amine vapors and produce radical anions in-situ through photo-induced electron transfer. The radical anions are protected against quenching by shielding effect in air and remain unobstructed in air for at least a month. Because of the high yield and stability of the radical anions, which are the basis for near-infrared photothermal conversion, the framework shows high near-infrared photothermal conversion efficiency (η = 52.3%). The work provides an efficient and simple method towards ambient stable radical anions and affords a promising material for photothermal therapy.
缺电子体系的自由基阴离子被广泛应用，但在暴露于空气中时容易被重新氧化。因此，在环境条件下稳定自由基阴离子具有重要意义，但仍然是一个科学挑战。在此，我们使用苝二酰亚胺制备了一种晶体金属有机骨架，在不进行广泛化学修饰的情况下稳定自由基阴离子。苝二酰亚胺的多孔、三维骨架可以捕获电子供体（如胺蒸气），并通过光诱导电子转移原位产生自由基阴离子。自由基阴离子通过屏蔽效应在空气中受到保护，并且在空气中至少一个月内不受阻碍。由于自由基阴离子的产率和稳定性很高，这是近红外光热转换的基础，因此该骨架表现出高的近红外光热转换效率（η=52.3%）。这项工作为环境稳定的自由基阴离子提供了一种高效简单的方法，并为光热治疗提供了一种有前途的材料。
