Compounds of s-Metals with Spin-Labeled Nitrophenol

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Abstract

A series of paramagnetic salts of s-elements (Li, Na, K, Rb, Cs) with deprotonated nitroxide radical, 2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide (L), were synthesized and isolated as crystals. According to X-ray diffraction data, these compounds are polymers of different dimensionality (CCDC nos. 2342497–2342506). As indicated by the results of quantum chemical calculations and magnetic measurements, weak antiferromagnetic exchange interactions predominate in the paramagnetic salts, with the interaction energy decreasing with increasing radius of the alkali metal ion.

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About the authors

O. V. Kuznetsova

International Tomography Center of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: bus@tomo.nsc.ru
Russian Federation, Novosibirsk

G. V. Romanenko

International Tomography Center of the Siberian Branch of the Russian Academy of Sciences

Email: bus@tomo.nsc.ru
Russian Federation, Novosibirsk

P. A. Chernavin

International Tomography Center of the Siberian Branch of the Russian Academy of Sciences

Email: bus@tomo.nsc.ru
Russian Federation, Novosibirsk

G. A. Letyagin

International Tomography Center of the Siberian Branch of the Russian Academy of Sciences

Email: bus@tomo.nsc.ru
Russian Federation, Novosibirsk

A. S. Bogomyakov

International Tomography Center of the Siberian Branch of the Russian Academy of Sciences

Email: bus@tomo.nsc.ru
Russian Federation, Novosibirsk

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Supplementary files

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2. Scheme 1. Structure of nitronylnitroxyl radicals LR and HL

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3. Fig. 1. Fragment of the LiL structure and the arrangement of ribbons in the crystal. Hereinafter, the carbon skeleton is shown in grey, O in red, N in blue, and Li in pink. The H atoms and CH3 groups of HL are not shown

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4. Fig. 2. Structure of [Li(H2O)(L)]-I (a) and [Li(H2O)(L)]-II (b) molecules and fragments of structures with the shortest contacts ONO...ONO (c, I) and (d, II)

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5. Fig. 3. Fragment of NaL structure (a) and layer (b)

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6. Fig. 4. Encirclement of atom K, anion L and a fragment of the layer in the KL structure

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7. Fig. 5. Environment L, atoms K and fragments of [KL(CH3CN)] (a), [KL(MeOH)] (b) and [KL(H2O)] (c) structures

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8. Fig. 6. Surrounding L, Rb atoms and fragment of the structure [RbL(H2O)]

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9. Fig. 7. Surrounding L, Cs atoms and fragment of CsL structure

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10. Fig. 8. Experimental dependences µeff(T) and fragments of the structure with the most effective channels of exchange interactions for LiL (a) and NaL (b)

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11. Fig. 9. Experimental dependences µeff(T) for [KL(H2O)] (a) and [RbL(H2O)] (b) and fragment of [KL(H2O)] structure (c) with the most effective channels of exchange interactions

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12. Fig. 10. Spin density distribution (surfaces labelled 0.0025 e/Å3) in the anion radicals L in the compounds LiL (a), NaL (b), [KL(H2O)] (c) and [RbL(H2O)] (d). The spin density with positive sign is shown in orange and with negative sign in purple. The H atoms were not shown

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