Imidazolium Salts with Heterometallic Complex Anions [Co₂Li₂(Piv)₈]²⁻: Synthesis, Structures, and Magnetic Properties

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Abstract

Imidazolium salts with complex anions [Co₂Li₂(Piv)₈]²⁻ are formed as undesirable products of the reactions of heterometallic compound [Co₂Li₂(Piv)₆(Py)₂] with N-heterocyclic carbenes ItBu and IPr. The study of the magnetic properties of complex (HItBu)₂[Co₂Li₂(μ₂-Piv)₆(Ƙ¹-Piv)₂] shows that this compound is a single molecule magnet. Slow magnetic relaxation in the complex occurs due to a combination of the direct and Raman mechanisms.

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About the authors

I. K. Rubtsova

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

P. N. Vasilyev

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

J. K. Voronina

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

M. A. Shmelev

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

N. N. Efimov

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

S. A. Nikolaevskii

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: sanikol@igic.ras.ru
Russian Federation, Moscow

I. L. Eremenko

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

M. A. Kiskin

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: sanikol@igic.ras.ru
Russian Federation, Moscow

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Supplementary files

Supplementary Files
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1. JATS XML
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2. Scheme 1.

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3. Fig. 1. Theoretical (red line) and experimental (blue line) diffraction patterns of a sample of complex I and their difference (gray line).

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4. Fig. 2. Structure of the dianions [Co₂Li₂(Piv)₈]²⁻ in I (a) and II (b) (thermal ellipsoids with a probability of 30%, methyl groups are not shown).

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5. Fig. 3. Fragment of packing I (intermolecular interactions C–H..O are shown by dotted lines, solvate molecules and hydrogen atoms at methyl groups are not shown).

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6. Fig. 4. Fragment of packing II (intermolecular interactions C–H..O and C–H⋅⋅⋅π are shown by dotted lines; hydrogen atoms not involved in intermolecular interactions are not shown).

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7. Fig. 5. Temperature dependence of χT for sample I (H = 5 kOe). The solid line is the calculated curve obtained using the PHI program.

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8. Fig. 6. M(H/T) (left) and M(H) (right) dependences at different temperatures for complex I. Solid lines are theoretical curves calculated using the PHI program.

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9. Fig. 7. Frequency dependences of the real (left) and imaginary (right) parts of the dynamic magnetic susceptibility of sample I at different temperatures; external magnetic field strength H = 500 Oe. Solid lines are approximations by the generalized Debye model.

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10. Fig. 8. Dependences of the relaxation time on the inverse temperature τ(1/T) of sample I. The red line is the approximation of the high-temperature part (2.25–2.75 K) by the Arrhenius equation. The blue line is the approximation by the sum of the Raman and direct mechanisms.

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