High-field EPR of copper()-nitroxide compound exhibiting three-step phase transition: structural insights from the field-induced sample orientation

Copper( ii )-nitroxide based Cu(hfac) 2 L R compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac) 2 L R are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exc...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2023-07, Vol.52 (27), p.9337-9345
Main Authors: Tumanov, Sergey V, Ponomaryov, Alexey N, Maryunina, Kseniya Yu, Bogomyakov, Artem S, Ovcharenko, Victor I, Zvyagin, Sergei A, Fedin, Matvey V, Veber, Sergey L
Format: Article
Language:English
Subjects:
Clusters
Copper
Electron paramagnetic resonance
Fourier transforms
High temperature
Jahn-Teller effect
Low temperature
Magnetic measurement
Magnetic properties
Microcrystals
Phase transitions
Single crystals
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Summary:Copper( ii )-nitroxide based Cu(hfac) 2 L R compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac) 2 L R are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exchange-coupled spin clusters Cu 2+ -O&z.rad;-N< or >N-&z.rad;O-Cu 2+ -O&z.rad;-N20 T) magnetic field. This effect was used to unveil the structural features of the low-temperature phase of Cu(hfac) 2 L MeMe , which were inaccessible using single-crystal X-ray diffraction (XRD) technique. In particular, high-field EPR allowed us to determine the relative direction of the Jahn-Teller axes in CuO 6 and CuO 4 N 2 units. Partial alignment of a polycrystalline paramagnetic sample in a high magnetic field enables the acquisition of important structural information inaccessible otherwise.
ISSN:1477-9226
1477-9234
DOI:10.1039/d3dt01297b