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

Polycyclic aromatic derivatives can trap 1O2 to form endoperoxides (EPOs) for O2 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 O2 capture and release. Metal–organic frameworks (MOFs) offer advantages in O2 binding, such as clear structure–performance relationships and precise controllability. Herein, we report the reversible binding of O2 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 1O2 to form EPOs and can be restored upon UV irradiation or heating to release O2. Furthermore, we confirm that photosensitizer‐incorporated anthracene‐based MOF are promising candidates for reversible O2 carriers controlled by switching Vis/UV irradiation. Capture and release: Controlled reversible binding of oxygen can be obtained through the chemical transformation between an anthracene‐based metal–organic framework (MOF) and the corresponding endoperoxide‐based MOF. With UV/Vis irradiation, the MOFs can be switched between trapping and releasing oxygen.