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Updated: Nov 25, 2025
Author Spotlight: Accelerating Discovery in Microporous Material Chemistry
Published on: October 6, 2023
Bridging Polyoxometalate-Based Mn4 Cubane Clusters with Inorganic Phosphates: Structural Transformation and Magnetic
Zhiwei Liu1, Qing Chang1, Weijie Wu1
1MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.
Abstract:
The mixed-valent tetramanganese MnIII3MnIV (Mn4) cubane clusters have been at the forefront of molecular magnetism and biomimetic catalysis research for decades. Incorporating robust polyoxometalates to Mn4 cubanes significantly improves their stability and aqueous solubility, while providing a great platform for studying their deposition onto selected surfaces during device fabrication. In this work, we discovered that the terminal carboxylate ligands in these polyoxometalate-based [MnIII3MnIVO4] magnetic clusters can be partially or completely replaced by inorganic phosphate/polyphosphate groups. This replacement leads to oligomeric aggregates of the Mn4 clusters. The magnetic data of the monomeric and oligomeric Mn4 clusters suggested that the introduction of inorganic phosphate bridges may not alter the S = 9/2 ground state of individual Mn4 clusters, although different magnetic behaviors, especially at low temperatures, were observed primarily because of intercluster interactions.
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