Artificial Mn 4 SrO 4 -Cluster Mimicking the Structural Changes of the Photosynthetic Oxygen-Evolving Center

作者：Changhui Chen, Zaining Wang, Mei-Lin Zhang, Kexin Jia, Feng Pan, Hongjun Fan, Su‐Yuan Xie, Jian‐Ren Shen, Ji‐Hu Su, Bing‐Wu Wang, Chunxi Zhang · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c14817 · 被引用次数：6 · 研究领域：Perovskite Materials and Applications、Electrocatalysts for Energy Conversion、Polyoxometalates: Synthesis and Applications

The oxygen-evolving center (OEC) of photosystem II (PSII) is characterized by a unique Mn 4 CaO 5 - or Mn 4 SrO 5 -cluster. Understanding the structure–function relationship and the catalytic mechanism of the OEC has been hindered by the lack of a rational model that precisely mimics both the static and dynamic structures of this biological cluster. Herein, we report a series of synthetic Mn 4 SrO 4 -clusters that closely mimic the main metal-oxide core, peripheral coordination sphere, redox properties, and the oxidation states of the four Mn ions in the Sr 2+ -containing OEC. Crystal structural measurements demonstrate that the presence of additional neutral ligands on Sr 2+ of the S 1 state Mn 4 SrO 4 -cluster can significantly modify the geometric conformation of the cluster, whereas the oxidation states and the dominant antiferromagnetic interactions of four Mn ions are largely undisturbed. EPR investigations and DFT calculations on the S 2 state Mn 4 SrO 4 -cluster demonstrate that the presence of additional neutral ligands can significantly affect the magnetic interactions of the cluster, converting the high-spin state giving rise to a g ≈ 4 EPR signal into a low-spin state with a g = 2 multiline EPR signal. Mass spectroscopic measurements show that a Mn 4 SrO 5 -cluster can be generated in solution from the synthetic Mn 4 SrO 4 -cluster. These observations provide chemical insights into the functional role of the redox-inactive metal ion (calcium or strontium), dynamic...