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Updated: Jul 22, 2025

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance
Published on: September 5, 2018
A Cationic Metal Glue Strategy for Expanding Paramagnetic Hetero-Multinuclear Metal-Oxo Clusters within
Takuo Minato1, Masahiro Sadakane1
1Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8527, Japan.
Abstract:
Precise structural design of large hetero-multinuclear metal-oxo clusters is crucial for controlling their large spin ground states and multielectron redox properties for application as a single-molecule magnet (SMM), molecular magnetic refrigeration, and efficient redox catalyst. However, it is difficult to synthesize large hetero-multinuclear metal oxo clusters as designed because the final structures are unpredictable when employing conventional one-step condensation reaction of metal cations and ligands. Herein, we report a "cationic metal glue strategy" for increasing the size and nuclearity of hetero-multinuclear metal-oxo clusters by using lacunary-type anionic molecular metal oxides (polyoxometalates, POMs) as rigid multidentate ligands. The employed method enabled the synthesis of {(FeMn4 )Mn2 Ln2 (FeMn4 )} oxo clusters (Ln=Gd, Tb, Dy, and Lu), which are the largest among previously reported paramagnetic hetero-multinuclear metal-oxo clusters in POMs and showed unique SMM properties. These clusters were synthesized by conjugating {FeMn4 } oxo clusters with Mn and Ln cations as glues in a predictable way, indicating that the "cationic metal glue strategy" would be a powerful tool to construct desired large hetero-multinuclear metal clusters precisely and effectively.
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