A large spin, magnetically anisotropic, octanuclear vanadium(<scp>iii</scp>) wheel

Sorolla, Maurice; Wang, Xiqu; Makarenko, Tatyana; Jacobson, Allan J.

doi:10.1039/c8cc08372j

Cited by 11 publications

(13 citation statements)

References 19 publications

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“…[(CH 3 ) 2 NH 2 ] 17.4 [SO 4 ] 0.7 [Cr III 8 (μ 2 -OH) 8 (μ 2 -SO 4 ) 16 ] and [(CH 3 ) 2 NH 2 ] 17.4 [SO 4 ] 0.7 [Fe III 8 (μ 2 -OH) 8 (μ 2 -SO 4 ) 16 ] are isostructural and contain the purely inorganic, octameric, ring-like, polyanionic cluster [M III (μ 2 -OH)(μ 2 -SO 4 ) 2 ] 8 16– , where M = Cr, Fe. These are analogous to the previously reported Ti(IV) and V(III) octanuclear molecular wheels. − As a representative, the structure of the eight-membered ferric wheel [Fe III 8 (OH) 8 (SO 4 ) 16 ] 16– is shown in Figure . The tilted octametallic wheels are stacked along the crystallographic a axis.…”

Section: Results and Discussionsupporting

confidence: 81%

“…While the vast majority of molecular wheels are bridged by organic ligands, those connected by sulfate ions are quite rare . So far, the {Ti 8 } and {V 8 } wheels are the only known examples of discrete inorganic rings with bridging sulfate ions. − Recently, we reported the anionic octanuclear wheel [V 8 (OH) 8 (SO 4 ) 16 ] 16– which has the largest ground-state magnetic spin known to date ( S t = 8) among homonuclear vanadium-based complexes . Extending our research to other 3d metals, we describe here the syntheses, crystal structures and magnetic properties of new octameric “chromic” and “ferric wheels” in which metal centers are linked by sulfato and hydroxo ligands.…”

Section: Introductionmentioning

confidence: 78%

“…18−20 Recently, we reported the anionic octanuclear wheel [V 8 (OH) 8 (SO 4 ) 16 ] 16− which has the largest ground-state magnetic spin known to date (S t = 8) among homonuclear vanadium-based complexes. 19 Extending our research to other 3d metals, we describe here the syntheses, crystal structures and magnetic properties of new octameric "chromic" and "ferric wheels" in which metal centers are linked by sulfato and hydroxo ligands. Anal.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Some highly disordered inter-ring species were treated with the program PLATON SQUEEZE. 24 Because of some undetermined guest atoms, the formulas of I and II were determined from the previous knowledge of the isostructural V-based compound, 19 chemical analyses, thermogravimetric analyses and charge balances. The final structure data in CIF format were deposited to the Cambridge Crystallographic Data Centre with the deposit numbers CCDC 1905775 and 1905776.…”

Section: ■ Introductionmentioning

confidence: 99%

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Sulfate-Bridged, Octanuclear Chromic and Ferric Wheels

et al. 2019

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Two new amine-templated transition metal-based sulfates, [(CH3)2NH2]17.4 [SO4]0.7 [MIII 8(μ2-OH)8(μ2-SO4)16] where M = Cr and Fe, have been synthesized via mild solvothermal synthesis. The compounds are isostructural and were refined in the monoclinic space group P21/n. They feature the rare sulfate-bridged inorganic molecular wheels [CrIII 8(OH)8(SO4)16]16– and [FeIII 8(OH)8(SO4)16]16–. In both the octanuclear chromic (J = −2.4 cm–1 based on Ĥ ex = −J · convention) and ferric wheels (J = −38.3 cm–1), the coupling between the adjacent metal ions is antiferromagnetic giving spin-singlet ground states. The variation in the magnitude of the exchange coupling constants is due to the differences in the superexchange mechanisms, namely, a π-pathway for the Cr- and a σ-pathway for the Fe-wheel cluster.

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Section: Results and Discussionsupporting

confidence: 81%

Section: Introductionmentioning

confidence: 78%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Sulfate-Bridged, Octanuclear Chromic and Ferric Wheels

et al. 2019

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“…Our results can be used to analyze the spin-flop transitions for other geometries and types of anisotropy, where the ground state is not necessarily uniform. We note that monitoring the curvature-dependent critical field, which is needed to induce the change of the magnetic state, provides a complementary method to determine material parameters for low-dimensional AFMs based on molecular magnets [35,36], DNA-based systems [37,38] or fabricated by means of atom-by-atom engineering [39,40].…”

Section: Discussionmentioning

confidence: 99%

Field-induced spin reorientation transitions in antiferromagnetic ring-shaped spin chains

Borysenko¹,

Sheka²,

Faßbender³

et al. 2022

Preprint

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Easy axis antiferromagnets are robust against external magnetic fields of moderate strength. Spin reorientations in strong fields can provide an insight into more subtle properties of antiferromagnetic materials, which are often hidden by their high ground state symmetry. Here, we investigate theoretically effects of curvature in ring-shaped antiferromagnetic achiral anisotropic spin chains in strong magnetic fields. We identify the geometry-governed helimagnetic phase transition above the spin-flop field between vortex and onion states. The curvature-induced Dzyaloshinskii-Moriya interaction results in the spin-flop transition being of first-or second-order depending on the ring curvature. Spatial inhomogeneity of the Néel vector in the spin-flop phase generates weak ferromagnetic response in the plane perpendicular to the applied magnetic field. Our work contributes to the understanding of the physics of curvilinear antiferromagnets in magnetic fields and guides prospective experimental studies of geometrical effects relying on spin-chain-based nanomagnets.

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A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides

Wan

Liu

et al. 2020

Chemistry A European J

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A SeO3‐centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K6H2[SeV10O28(SeO3)3]⋅14 H2O (1) was isolated by one‐pot reaction of KVO3 and SeO2 under acidic conditions. X‐ray studies revealed that it comprised a single {VO5}‐capped trivacant B‐α‐type Keggin ion [SeV9O33(VO)]14− with its lacunary sites decorated by three {SeO3} pyramids. Interestingly, this new basic hetero‐POV building block was further used as a precursor to assemble with different transition‐metal (TM) ions, yielding a series of TM‐sandwiched POVs K6H8[(SeV10O28(SeO3)3)2(M(H2O)4)]⋅24 H2O (M2+=Mn2+ (2), Co2+ (3), Zn2+ (4)). All four compounds were characterized by single‐crystal X‐ray structure analysis, IR, X‐ray photoelectron spectroscopy (XPS), EPR, and 51V NMR spectroscopy. Importantly, three TM‐sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.

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A large spin, magnetically anisotropic, octanuclear vanadium(iii) wheel

Abstract: A large spin, magnetically anisotropic, ferromagnetically coupled octanuclear vanadium(iii) wheel-like cluster has been synthesized.

Cited by 11 publications

References 19 publications

Sulfate-Bridged, Octanuclear Chromic and Ferric Wheels

Sulfate-Bridged, Octanuclear Chromic and Ferric Wheels

Field-induced spin reorientation transitions in antiferromagnetic ring-shaped spin chains

A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides

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