Structural Transformation in Metal–Organic Frameworks for Reversible Binding of Oxygen

Abstract Polycyclic aromatic derivatives can trap 1 O 2 to form endoperoxides (EPOs) for O 2 storage and as sources of reactive oxygen species. However, these materials suffer from structural amorphism, which limit both practical applications and fundamental studies on their structural optimization for O 2 capture and release. Metal–organic frameworks (MOFs) offer advantages in O 2 binding, such as clear structure–performance relationships and precise controllability. Herein, we report the reversible binding of O 2 is realized via the chemical transformation between anthracene‐based and the corresponding EPO‐based MOF. It is shown that anthracene‐based MOF, the framework featuring linkers with polycyclic aromatic structure, can rapidly trap 1 O 2 to form EPOs and can be restored upon UV irradiation or heating to release O 2 . Furthermore, we confirm that photosensitizer‐incorporated anthracene‐based MOF are promising candidates for reversible O 2 carriers controlled by switching Vis/UV irradiation.