Photochargeable Mn‐Based Metal–Organic Framework and Decoupled Photocatalysis.

Designing multifunctional materials that mimic the light‐dark decoupling of natural photosynthesis is a key challenge in the field of energy conversion. Herein, we introduce MnBr‐253, a precious metal‐free metal–organic framework (MOF) built on Al nodes, bipyridine linkers and MnBr(CO)3(bipyridine) complexes. Upon irradiation, MnBr‐253 colloids demonstrate an electron photocharging capacity of ~42 C ⋅ g−1MOF, with state‐of‐the‐art photocharging rate (1.28 C ⋅ s−1 ⋅ g−1MOF) and incident photon‐to‐electron conversion efficiency of ~9.4 % at 450 nm. Spectroscopic and computational studies support effective electron accumulation at the Mn complex while high porosity and Mn loading account for the notable electron storage performance. The charged MnBr‐253 powders were successfully applied for hydrogen evolution under dark conditions thus emulating the light‐decoupled reactivity of photosynthesis. [ABSTRACT FROM AUTHOR]