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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| Vydáno v: | Journal of the American Chemical Society Ročník 138; číslo 50; s. 16493 |
|---|---|
| Hlavní autoři: | , , , , , , , , , , , , |
| Médium: | Journal Article |
| Jazyk: | angličtina |
| Vydáno: |
United States
21.12.2016
|
| ISSN: | 1520-5126, 1520-5126 |
| On-line přístup: | Zjistit podrobnosti o přístupu |
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| Shrnutí: | 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. |
|---|---|
| Bibliografie: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1520-5126 1520-5126 |
| DOI: | 10.1021/jacs.6b10544 |