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Title

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

Authors
Lannes, Anthony
Tommasino, Jean Bernard
Chiriac, Rodica
Toche, François
Khrouz, Lhoussain
Molton, Florian
Duboc, Carole
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Published in Journal of the American Chemical Society. 2016, vol. 138, no. 50, p. 16493-16501
Abstract The manganese-nitronyl-nitroxide two dimensional coordination polymer {[Mn2(NITIm)3]ClO4}n (1) (NITImH = 2-(2-imidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-3-oxide-1-oxyl) undergoes an unusual hysteretic thermoinduced 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 NITImRed2-). Upon cooling, the high-temperature species {[MnII2(NITIm)3]ClO4}n (1HT) turns into the low-temperature species {[MnIII2(NITImRed)2(NITIm)]ClO4}n (1LT) 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) an emission (XES) and Electron Paramagnetic Resonance (EPR) spectroscopies in the solid-state.
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Other version: http://pubs.acs.org/doi/abs/10.1021/jacs.6b10544
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Research group Groupe Hauser
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LANNES, Anthony et al. Room Temperature Magnetic Switchability Assisted by Hysteretic Valence Tautomerism in a Layered Two-Dimensional Manganese-Radical Coordination Framework. In: Journal of the American Chemical Society, 2016, vol. 138, n° 50, p. 16493-16501. https://archive-ouverte.unige.ch/unige:90821

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Deposited on : 2017-01-04

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