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Updated: May 8, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
A dinuclear cobalt complex featuring unprecedented anodic and cathodic redox switches for single-molecule magnet
Skye Fortier1, Jennifer J Le Roy, Chun-Hsing Chen
1Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
Abstract:
One-electron oxidation or reduction of the paramagnetic dinuclear Co(II) complex dmp2Nin{Co[N(SiMe3)2]}2 (1; dmp2Nin(2-) = bis(2,6-dimethylphenyl)nindigo), by fully reversible chemical or electrochemical methods, generates the radical salts [1(OEt2)](+) and [1](-), respectively. Full structural and magnetic analyses reveal the locus of the redox changes to be nindigo-based, thus giving rise to ligand-centered radicals sandwiched between two paramagnetic and low-coordinate Co(II) centers. The presence of these sandwiched radicals mediates magnetic coupling between the high-spin (S = 3/2) cobalt ions, which gives rise to single-molecule magnet (SMM) activity in both the oxidized ([1(OEt2)](+)) and reduced ([1](-)) states. This feature represents the first example of a SMM exhibiting fully reversible, dual "ON/OFF" switchability in both the cathodic and anodic states.
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