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Updated: Mar 10, 2026

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
A Redox-Induced Spin-State Cascade in a Mixed-Valent Fe3 (μ3 -O) Triangle
Evgen V Govor1, Karrar Al-Ameed2,3, Indranil Chakraborty4
1Department of Chemistry and Biochemistry and the Biomedical Sciences Institute, Florida International University, 11200 SW 8th Street, Miami, FL, 33199, USA.
Abstract:
One-electron reduction of a pyrazolate-bridged triangular Fe3 (μ3 -O) core induces a cascade wherein all three metal centers switch from high-spin Fe3+ to low-spin Fe2.66+ . This hypothesis is supported by spectroscopic data (1 H-NMR, UV-vis-NIR, infra-red, 57 Fe-Mössbauer, EPR), X-ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters. This is, to the best of our knowledge, the first example of a one-electron redox event causing concerted change in multiple iron centers.
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