Stable radical anions generated from a porous perylenediimide metal-organic framework for boosting near-infrared photothermal conversion.

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.