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New sterically hindered disubstituted imine derivatives of (thia)calix[4]arenes bearing bulky tert-butyl groups at the lower rim: synthesis, structures, and complexation ability toward CoII and NiII cations in solution

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Abstract

New macrocyclic Schiff bases, lower rim disubstituted imine derivatives of thia- and calix[4]arenes 7 and 8 adopted in a cone stereoisomeric conformation, bearing two tert-butyl substituents grafted to iminophenol coordinating sites, and containing a spacer composed of two methylene bridges were synthesized. The prepared compounds were characterized by a complex of physicochemical methods in solution (1H/13C NMR spectroscopy, MALDI TOF mass spectrometry) and in the crystalline phase (IR spectroscopy, single-crystal X-ray diffraction (XRD)). In crystals calix[4]arene 7 forms a solvate in which acetonitrile or methanol molecules are included into the macrocycle cavity, whereas the crystals of thiacalix[4]arene 8 contain no solvent molecules. The difference in the conformational behavior of the macrocyclic platform was evidenced when comparing the crystal structures of calix[4]arene 7 and thiacalix[4]arene 8. The stoichiometry and the logarithm and stability constant values of the corresponding complexes of the synthesized macrocyclic Schiff bases with 3d-metal cations (CoII, NiII) in solution were determined using spectrophotometry titration. When interacting with CoII cations, compound 7 forms complexes with stoichiometry Lig: M = 1: 1 and 1: 2 (Lig is ligand, and M is metal). In the case of compound 8, complexes with the stoichiometry Lig: M = 1: 4, as well as 1: 2, are observed, which presumably indicates the involvement of “soft” sulfur atoms in the interaction with the metal cations. The replacement of CoII cations by NiII resulted in the formation in the solution of complexes with the stoichiometry Lig: M = 2: 1, 1: 1 and Lig: M = 1: 1, 1: 2 for compounds 7 and 8, respectively.

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Acknowledgments

The authors are grateful to the Collective Spectral Analytical Center of Physicochemical Research of Structure, Properties, and Composition of Substances and Materials at the Federal Research Center “Kazan Scientific Center of the Russian Academy of Sciences” for technical support of the conducted studies.

Funding

This work was financially supported by the Russian Science Foundation (Project No. 22-73-10139).

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Authors and Affiliations

  1. A. E. Arbuzov Institute of Organic and Physical Chemistry, Federal Research Center “Kazan Scientific Center of the Russian Academy of Sciences,”, 8 ul. Akad. Arbuzova, 420088, Kazan, Russian Federation

    I. V. Strelnikova, A. S. Ovsyannikov, F. B. Gabdrakhmanova, A. S. Agarkov, A. T. Gubaidullin, A. R. Khamatgalimov & S. E. Solovieva

  2. Kazan Federal University, 18 ul. Kremlevskaya, 420008, Kazan, Russian Federation

    I. D. Shutilov & I. S. Antipin

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  1. I. V. Strelnikova
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Correspondence to A. S. Ovsyannikov.

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Dedicated to the memory of Academician of the Russian Academy of Sciences A. I. Konovalov (1934—2021) on the occasion of his 90th anniversary.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 73, No. 3, pp. 653–668, March, 2024.

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Strelnikova, I.V., Shutilov, I.D., Ovsyannikov, A.S. et al. New sterically hindered disubstituted imine derivatives of (thia)calix[4]arenes bearing bulky tert-butyl groups at the lower rim: synthesis, structures, and complexation ability toward CoII and NiII cations in solution. Russ Chem Bull 73, 653–668 (2024). https://doi.org/10.1007/s11172-024-4175-0

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