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Updated: Jun 18, 2025
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Osmium(III) Acetylacetonate and Its Missing Polymorph: A Magnetic and Structural Investigation
Arsen Raza1,2, Laura Chelazzi3, Samuele Ciattini3
1Department of Chemistry "Ugo Schiff", DICUS and INSTM Research Unit, University of Florence, Via della Lastruccia 3-13, 50019 Sesto Fiorentino, Florence, Italy.
Abstract:
Despite the potential for their application, the magnetic behavior of complexes containing 4d and 5d metal ions is underexplored, evidencing the need for benchmark multi-technique studies on simple molecules. We report here a structural and magnetic study on osmium(III) acetylacetonate [Os(acac)3]. X-ray single crystal diffraction did not allow us to determine the structure of the β-polymorph of [Os(acac)3]. The combined magnetic (dc magnetic measurements on powder and cantilever torque magnetometry on single crystal) and spectroscopic (electron paramagnetic resonance, EPR) characterization is here used to provide further evidence that its structure is indeed the one of the orthorhombic "missing polymorph", analogous to the ruthenium(III) derivative. Our study shows that all acetylacetonate complexes of the eighth group of the periodic table show dimorphism and are isomorphic. The EPR characterization allowed the experimental assessment of the easy axis nature of the ground doublet and the determination of the first hyperfine coupling in an osmium complex. Torque magnetometry, applied here for the first time on an osmium-based molecule, determined the orientation of the easy axis along the pseudo C3 axis of the complex. Ac magnetometric measurements revealed in-field slow relaxation of the magnetization further slowed by the suppression of dipolar fields via magnetic dilution in the isostructural gallium(III) analogue.
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