Room Temperature Magnetic Switchability Assisted by Hysteretic Valence Tautomerism in a Layered Two-Dimensional Manganese-Radical Coordination Framework

The manganese-nitronyl-nitroxide two-dimensional coordination polymer {[Mn (NITIm) ]ClO } (1) (NITImH = 2-(2-imidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-3-oxide-1-oxyl) undergoes an unusual hysteretic thermo-induced valence tautomeric transition near room temperature, during which the manganese(I...

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Veröffentlicht in:Journal of the American Chemical Society Jg. 138; H. 50; S. 16493
Hauptverfasser: Lannes, Anthony, Suffren, Yan, Tommasino, Jean Bernard, Chiriac, Rodica, Toche, François, Khrouz, Lhoussain, Molton, Florian, Duboc, Carole, Kieffer, Isabelle, Hazemann, Jean-Louis, Reber, Christian, Hauser, Andreas, Luneau, Dominique
Format: Journal Article
Sprache:Englisch
Veröffentlicht: United States 21.12.2016
ISSN:1520-5126, 1520-5126
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Zusammenfassung:The manganese-nitronyl-nitroxide two-dimensional coordination polymer {[Mn (NITIm) ]ClO } (1) (NITImH = 2-(2-imidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-3-oxide-1-oxyl) undergoes an unusual hysteretic thermo-induced valence tautomeric transition near room temperature, during which the manganese(II) ions are oxidized to manganese(III) and two of the three deprotonated radicals (NITIm ) are reduced to their diamagnetic aminoxyl form (denoted NIT ). Upon cooling, the high-temperature species {[Mn (NITIm) ]ClO } (1 ) turns into the low-temperature species {[Mn (NIT ) (NITIm)]ClO } (1 ) around 274 K, while on heating the process is reversed at about 287 K. This valence tautomeric phenomenon is supported by temperature-dependent magnetic susceptibility measurements, differential scanning calorimetry (DSC), crystal structure determination, UV-vis absorption, X-ray absorption (XAS), and emission (XES) and electron paramagnetic resonance (EPR) spectroscopies in the solid state.
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ISSN:1520-5126
1520-5126
DOI:10.1021/jacs.6b10544