[MnIII(Schiff Base)]3[ReIV(CN)7], Highly Anisotropic 3D Coordination Framework: Synthesis, Crystal Structure, Magnetic Investigations, and Theoretical Analysis

[MnIII(Schiff Base)]3[ReIV(CN)7], Highly Anisotropic 3D Coordination Framework: Synthesis, Crystal Structure, Magnetic Investigations, and Theoretical Analysis Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2014, Volume: 53, Number: 19, Pages: 10217-10231 Pages count : 15 DOI: 10.1021/ic501247x

Authors

Samsonenko Denis G. ^1,2 , Paulsen Carley ³ , Lhotel Elsa ³ , Mironov Vladimir S. ⁵ , Vostrikova Kira E. ^4,1

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, SB RAS, 3 Lavrentiev Avenue, Novosibirsk 630090, Russia
2	Novosibirsk State University, 2 Pirogova Street, Novosibirsk 630090, Russia
3	Institut Néel, CNRS & Université Joseph Fourier, 25 Rue des Martyrs, 38042 Grenoble, France
4	Laboratoire des Multimatériaux et Interfaces, UMR 5615, Université Claude Bernard Lyon 1, Bat. Chevreul, 43 bd du 11 Novembre 1918, 69622 Villeurbanne, France
5	IC RAS - A. V. Shubnikov Institute of Crystallography (Leninskii prospekt 59, Moscow, 119333 - Russia)

A new highly anisotropic coordination heterobimetallic polymer [MnIII(Schiff-base)]3[ReIV(CN)7] was synthesized and characterized structurally and magnetically. The single crystal X-ray analysis has revealed that this is the first framework among the complexes composed of homoleptic cyanometallate and MnIII complex of the tetradentate Schiff base ligand. A formation of 3D assembly is possible due to both the pentagonal bipyrimidal geometry of the cyanometallate unit and suitable size of constituents: [Re(CN)7]3– and [MnIII(acacen)]+, where acacen = N,N′-ethylenebis(acetylacetoneiminato). The powder and crystal magnetic studies show that the compound undergoes an antiferromagnetic ordering of a complicated character below Neel temperature of 13 K, and exhibits a metamagnetic behavior and strong magnetic anisotropy similar to those observed in related 3D MnII–[Mo(CN)7]4– systems. Unusual magnetic properties of [MnIII(acacen)]3[ReIV(CN)7] (1) originate from an interplay of Re–Mn anisotropic spin coupling and ZFS effect of MnIII ions with a noncollinear orientation of the local magnetic axes in the cyano-bridged 3D network. A theoretical model of anisotropic spin coupling between orbitally degenerate [ReIV(CN)7]3– complexes and MnIII ions is developed, and specific microscopic mechanisms of highly anisotropic spin coupling in ReIV–CN–MnIII linkages in complex 1 are analyzed in detail.

Samsonenko D.G. , Paulsen C. , Lhotel E. , Mironov V.S. , Vostrikova K.E.
[MnIII(Schiff Base)]3[ReIV(CN)7], Highly Anisotropic 3D Coordination Framework: Synthesis, Crystal Structure, Magnetic Investigations, and Theoretical Analysis
Inorganic Chemistry. 2014. V.53. N19. P.10217-10231. DOI: 10.1021/ic501247x Scopus OpenAlex

Scopus:	2-s2.0-84907821892
OpenAlex:	W2318803599

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