Synthesis, structure and magnetic properties of the monocapped 3d-metal(II) tris-N,S-heterocyclooximates: the design of cobalt pseudoclathrochelate with a single-ion magnet behavior

Synthesis, structure and magnetic properties of the monocapped 3d-metal(II) tris-N,S-heterocyclooximates: the design of cobalt pseudoclathrochelate with a single-ion magnet behavior Full article

Journal

Polyhedron
ISSN: 0277-5387

Output data

Year: 2026, Volume: 284, Article number : 117860, Pages count : DOI: 10.1016/j.poly.2025.117860

Authors

Belova Svetlana A. ¹ , Belov Alexander S. ^1,2 , Lebed Ekaterina G. ¹ , Danshina Anastasia A. ¹ , Dorovatovskii Pavel V. ³ , Bogomyakov Artem S. ⁴ , Dmitriev Alexey I. ⁵ , Zhidkov Mikhail V. ⁵ , Korchagin Denis V. ⁵ , Voloshin Yan Z. ^1,2

Affiliations

1	Nesmeyanov Institute of Organoelement Compounds of RAS, 28-1 Vavilova St., 119334 Moscow, Russia
2	Kurnakov Institute of General and Inorganic Chemistry of RAS, 31 Leninsky Prosp., 119991 Moscow, Russia
3	National Research Center Kurchatov Institute, 1 Kurchatova Pl., 123098 Moscow, Russia
4	International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a, Institutskaya Str., 630090 Novosibirsk, Russia
5	Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russia

Template condensation of 4-acetylthiazoloxime as a chelating ligand synthon and phenylboronic acid as a Lewis-acidic cross-linking agent on the nickel(II) ion using its perchlorate salt gave the ionic associate of phenylboron-monocapped nickel(II)-centered tris-thiazoloximate cation with ClO4− counter-anion. That with metal(II) chlorides (M2+ = Fe2+, Co2+, Ni2+, Mn2+ and Zn2+) as the sources of M2+ ions afforded the corresponding chloride-H-bonded pseudomacrobicyclic intracomplexes. As follows from the single-crystal X-ray diffraction data, their pseudomacrobicyclic structures are formed by Csingle bondH…Cl− contacts with three N,S-heterocyclic groups of thiazoloximate synthons. Fe(II), Co(II) and Zn(II) ions are located in the centers of their trigonal-prismatic MN6-coordination polyhedra, while geometry of NiN6-polyhedra is intermediate between a trigonal prism and trigonal antiprism. All the prepared metal(II) pseudoclathrochelates were also characterized using elemental analysis, PXRD, MALDI-TOF MS, UV–vis and NMR methods. According to the magnetometry and X-ray diffraction data, their metal(II) ions are in high-spin states. The ac and dc magnetic studies, supported by the SA-CASSCF/NEVPT2 quantum chemical calculations, revealed that a given cobalt(II) pseudoclathrochelate exhibits the strong uniaxial magnetic anisotropy due to the unquenched angular orbital momentum. It also demonstrates a zero-field single-molecule magnet behavior with quantum tunneling of the magnetization as the only one magnetically sensitive relaxation mechanism.

Belova S.A. , Belov A.S. , Lebed E.G. , Danshina A.A. , Dorovatovskii P.V. , Bogomyakov A.S. , Dmitriev A.I. , Zhidkov M.V. , Korchagin D.V. , Voloshin Y.Z.
Synthesis, structure and magnetic properties of the monocapped 3d-metal(II) tris-N,S-heterocyclooximates: the design of cobalt pseudoclathrochelate with a single-ion magnet behavior
Polyhedron. 2026. V.284. 117860 . DOI: 10.1016/j.poly.2025.117860 WOS Scopus OpenAlex

Submitted:	Jul 9, 2025
Accepted:	Oct 24, 2025
Published online:	Nov 4, 2025
Published print:	Feb 1, 2026

Web of science:	WOS:001616860000002
Scopus:	2-s2.0-105021016961
OpenAlex:	W4415880379

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