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Complexes of CuII with nitroxides and their magnetochemical behavior

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Abstract

The synthesis, structures, and magnetochemical data for the heterospin chain polymer complexes Cu(hfac)2LAll and Cu(hfac)2LBu·0.5Solv, where hfac is the hexafluoroacetylacetonate anion, LAll and LBu are 2-(1-allyl-1H-pyrazol-4-yl)- and 2-(1-butyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyls, respectively, Solv is isopropylbenzene or tert-butylbenzene, were described. These polycrystalline solids were found to exhibit similar magnetic anomalies. Thus, the effective magnetic moment first decreases and then increases with temperature, resulting in the specific minimum in the curve μeff(T). The study of the magneto-structural correlations showed that the appearance of the minimum is attributed to different factors. For Cu(hfac)2LAll, this is the phase transition accompanied by the structural rearrangement of the exchange cluster >N—·O—CuII—O·—N<, which leads to a change in the energy of the exchange interaction between the unpaired electrons of the paramagnetic centers. By contrast, for Cu(hfac)2LBu·0.5PriPh and Cu(hfac)2LBu·0.5ButPh, the appearance of the minimum is a consequence of the coexistence of exchange interaction energies with opposite signs, while the structure of the solid phase remains unchanged.

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Authors and Affiliations

  1. International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090, Novosibirsk, Russian Federation

    K. Yu. Maryunina, G. V. Romanenko, S. V. Fokin, A. S. Bogomyakov & V. I. Ovcharenko

  2. Kazan National Technological University, 68 ul. K. Marksa, 420015, Kazan, Russian Federation

    E. M. Zueva

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  1. K. Yu. Maryunina
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  2. G. V. Romanenko
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  3. E. M. Zueva
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  4. S. V. Fokin
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  5. A. S. Bogomyakov
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  6. V. I. Ovcharenko
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Correspondence to V. I. Ovcharenko.

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Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 60th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2337—2344, Novemer, 2013.

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Maryunina, K.Y., Romanenko, G.V., Zueva, E.M. et al. Complexes of CuII with nitroxides and their magnetochemical behavior. Russ Chem Bull 62, 2337–2344 (2013). https://doi.org/10.1007/s11172-013-0339-z

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  • DOI: https://doi.org/10.1007/s11172-013-0339-z

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