Elucidating the Oxygen-Activation Mechanism in Nonheme Mn II -, Fe II -, or Co II -Containing MOFs Mimicking Fe II /2-Oxoglutarate-Dependent Complexes

Journal article

A Fe/Zn metal–organic framework (MOF) that mimics the FeII/2-oxoglutarate-dependent complex (FeII/2-OGDC) was reported previously, but its oxygen-activation mechanism remains unclear. In the present research, density functional theory (DFT) calculations were used to study this Fe-based system and its Mn- and Co-substituted analogues. We found that all three systems follow the general oxygen-activation chemistry of FeII/2-OGDC but show clear metal-dependent differences. The Fe and Co systems generate high-spin TMIV–oxo complexes, whereas the Mn system forms high-spin MnIII-oxyl complexes. The energy profiles further show that the formation of the key oxidizing intermediate is more favorable in the Fe and Mn systems than in the Co system. Overall, this work explains how changing the metal center affects oxygen activation in MOF-based enzyme mimics and highlights Mn as a more promising substitute for Fe than Co.

Authors: Huang, Z; Li, Y; Zhang, X; Chen, X; Xu, J

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Inorganic Chemistry
• Volume: 65
• Issue: 22
• Pages: 12206-12219
• Publication date: 2026-05-21
• Acceptance date: 2026-05-18
• DOI: 10.1021/acs.inorgchem.6c00307
• EISSN: 1520-510X
• ISSN: 0020-1669
• Language: English
• Keywords: Oxidizing agent; Mechanism (biology); Metal; Manganese; Oxygen; Work (physics)