Synthesis, crystal structure and NMR-study new mononuclear paramagnetic Er (III) complex based on imine derivatives of thiacalix[4]arene

Synthesis, crystal structure and NMR-study new mononuclear paramagnetic Er (III) complex based on imine derivatives of thiacalix[4]arene Full article

Journal

Inorganica Chimica Acta
ISSN: 0020-1693 , E-ISSN: 1873-3255

Output data

Year: 2023, Volume: 545, Pages: 121267 Pages count : 1 DOI: 10.1016/j.ica.2022.121267

Tags

erbium (III), Calix[4] arene, Schiff base Crystal structure, dynamic NMRC hemical exchange

Authors

Zapolotsky Eugeny N. ¹ , Babailov Sergey P. ¹ , Kniazeva Mariia V. ² , Strelnikova Yuliia V. ³ , Ovsyannikov Alexander S. ² , Gubaidullin Aidar T. ² , Solovieva Svetlana E. ² , Antipin Igor S. ³ , Fomin Eduard S. ⁴ , Chuikov Igor P. ⁵

Affiliations

1	Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the RAS
2	A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of Russian Academy of Sciences
3	Kazan Federal University
4	Institute of Cytology and Genetics of Siberian Branch of the Russian Academy of Sciences
5	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

The synthesis, crystal structure and NMR-study of new paramagnetic Er (III) complex based on imine derivatives of thiacalix[4]arene was carried out. Temperature dependences of the 1H NMR spectra of complex Er(III) and calix[4]arene with N-contained substituents (I) have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Two kinds of molecular dynamics in I are reported for the CDCl3 solution. The first one conformational dynamics is conditioned by the pinched cone A ↔ pinched cone B interconversion with activation free energy ΔG≠(298 K) = 40 ± 3 kJ/mol (observed at low temperature). The second one dynamics is connected with rearrangements in coordination environment (with ΔG≠(298 K) = 58 ± 3 kJ/mol). Due to substantial temperature dependence of paramagnetic shifts, the complex I can be considered as NMR thermosensor reagent for local temperature monitoring. Owing to the large magnetic moments typical for many Ln-ions and especially high value of magnetic anisotropy for Er cation (III) adopting capped trigonal prismatic geometry of coordination sphere one may expect that 1-Er can potentially exhibit SMM behavior.

Zapolotsky E.N. , Babailov S.P. , Kniazeva M.V. , Strelnikova Y.V. , Ovsyannikov A.S. , Gubaidullin A.T. , Solovieva S.E. , Antipin I.S. , Fomin E.S. , Chuikov I.P.
Synthesis, crystal structure and NMR-study new mononuclear paramagnetic Er (III) complex based on imine derivatives of thiacalix[4]arene
Inorganica Chimica Acta. 2023. V.545. P.121267. DOI: 10.1016/j.ica.2022.121267 WOS РИНЦ

Submitted:	Sep 6, 2022
Accepted:	Oct 20, 2022
Published online:	Nov 1, 2022
Published print:	Nov 5, 2022

Web of science	WOS:000895938800003
Elibrary	54719440
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