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Diversity of Structural Motifs in Cu(hfac)2 Complexes with Spin-Labeled Polyalkylpyrazoles

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Abstract

The extension of a series of polyalkylpyrazolyl-substituted 2-imidazoline nitronyl nitroxide radicals LR1/R2/R3 (R = Me, Et, Pr, Bu) enables the synthesis of a number of coordination polymers based on copper(II) bis(hexafluoroacetylacetonate) Cu(hfac)2 with LR1/R2/R3. As compared to breathing crystals (Cu(hfac)2 complexes with monoalkyl-substituted nitroxides LR1 with bridging μ2-O,N coordination), the introduction of the second substituent LR1/R2 into the pyrazole ring allows the performance of the tritopic function of the paramagnetic ligand (μ3-O,O,N) and the formation of 1D and 2D polymers with original structures and different combinations of [CuO6], [CuO5N], [CuO4N2], and [CuO5] coordination cores. Only molecular complexes are obtained with single 3-substituted nitroxide LR1/R2/R3–LMe3. The single crystal X-ray diffraction study of the structures of these compounds shows that as in the case of LMe3, an increase in the size of one of substituents in LR1/R2 to Pr or Bu causes an increase in distances between paramagnetic centers in two- and three-spin exchange clusters, and correspondingly, spin transitions are absent.

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Funding

The work was supported by the Russian Science Foundation (grant 23-13-00014).

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Authors and Affiliations

  1. International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    S. V. Fokin, E. T. Chubakova, S. E. Tolstikov, G. V. Romanenko, K. A. Smirnova, A. S. Bogomyakov & V. I. Ovcharenko

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  1. S. V. Fokin
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  2. E. T. Chubakova
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  3. S. E. Tolstikov
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  6. A. S. Bogomyakov
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  7. V. I. Ovcharenko
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Correspondence to S. V. Fokin.

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Russian Text © The Author(s), 2024, published in Zhurnal Strukturnoi Khimii, 2024, Vol. 65, No. 2, 121584.https://doi.org/10.26902/JSC_id121584

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Fokin, S.V., Chubakova, E.T., Tolstikov, S.E. et al. Diversity of Structural Motifs in Cu(hfac)2 Complexes with Spin-Labeled Polyalkylpyrazoles. J Struct Chem 65, 230–242 (2024). https://doi.org/10.1134/S0022476624020021

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