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Non-collinear magnetism in the post-perovskite thiocyanate frameworks CsM(NCS)₃.

ABSTRACT: AMX₃ compounds are structurally diverse, a notable example being the post-perovskite structure which adopts a two-dimensional framework with corner- and edge-sharing octahedra. Few molecular post-perovskites are known and of these, none have reported magnetic structures. Here we report the synthesis, structure and magnetic properties of molecular post-perovskites: CsNi(NCS)₃, a thiocyanate framework, and two new isostructural analogues CsCo(NCS)₃ and CsMn(NCS)₃. Magnetisation measurements show that all three compounds undergo magnetic order. CsNi(NCS)₃ (Curie temperature, T _C = 8.5(1) K) and CsCo(NCS)₃ (T _C = 6.7(1) K) order as weak ferromagnets. On the other hand, CsMn(NCS)₃ orders as an antiferromagnet (Néel temperature, T _N = 16.8(8) K). Neutron diffraction data of CsNi(NCS)₃ and CsMn(NCS)₃, show that both are non-collinear magnets. These results suggest molecular frameworks are fruitful ground for realising the spin textures required for the next generation of information technology.

SUBMITTER: Geers M

PROVIDER: S-EPMC10055978 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Non-collinear magnetism in the post-perovskite thiocyanate frameworks CsM(NCS)3.

Geers Madeleine M Lee Jie Yie JY Ling Sanliang S Fabelo Oscar O Cañadillas-Delgado Laura L Cliffe Matthew J MJ

Chemical science 20230221 13

AMX3 compounds are structurally diverse, a notable example being the post-perovskite structure which adopts a two-dimensional framework with corner- and edge-sharing octahedra. Few molecular post-perovskites are known and of these, none have reported magnetic structures. Here we report the synthesis, structure and magnetic properties of molecular post-perovskites: CsNi(NCS)3, a thiocyanate framework, and two new isostructural analogues CsCo(NCS)3 and CsMn(NCS)<su ...[more]

PMID: 37006672

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Project description:The new heterometallic compounds, [{Cu(pn)2}2Ni(NCS)6]n·2nH2O (1), [{CuII(trien)}2Ni(NCS)6CuI(NCS)]n (2) and [Cu(tren)(NCS)]4[Ni(NCS)6] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [CuII(tren)]2+ antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {NiIICuII2} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)3]3- linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 → 2 → 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment.

Dataset Information

Non-collinear magnetism in the post-perovskite thiocyanate frameworks CsM(NCS)₃.

Publications

Non-collinear magnetism in the post-perovskite thiocyanate frameworks CsM(NCS)<sub>3</sub>.

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