Tetraimidoschwefelsäure H2S(NtBu)4– isovalenzelektronisch zu H2SO4

Jung, Jochen; Münch, Annika; Herbst‐Irmer, Regine

doi:10.1002/ange.202014426

“…[17] We have been already successful employing those ligands to d-block SMMs with the [MeS (NtBu)] À ligand in [Co{(NtBu) 3 SMe} 2 ], (with U eff = 75 cm À 1 , T B = 2.6 K and a hysteresis loop at 2 K), [18] accompanying of a series of complexes with the [S(NtBu) 4 ] 2À anion. [19,20] This fuelled the idea to transfer the ligand concept to f-block metals. First results are presented in here.…”

Section: Introductionmentioning

confidence: 99%

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Jung

¹

,

Benner

²

,

Herbst‐Irmer

³

et al. 2021

Chemistry A European J

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Lanthanide ions are particularly well-suited for the design of single-molecule magnets owing to their large unquenched orbital angular momentum and strong spin-orbit coupling that gives rise to high magnetic anisotropy. Such nanoscopic bar magnets can potentially revolutionize highdensity information storage and processing technologies, if blocking temperatures can be increased substantially. Exploring non-classical ligand scaffolds with the aim to boost the barriers to spin-relaxation are prerequisite. Here, the syn-thesis, crystallographic and magnetic characterization of a series of each isomorphous mono-and dinuclear lanthanide (Ln = Gd, Tb, Dy, Ho, Er) complexes comprising tetraimido sulfate ligands are presented. The dinuclear Dy complex [{(thf) 2 Li(NtBu) 2 S(tBuN) 2 DyCl 2 } 2 • ClLi(thf) 2 ] (1c) shows true signatures of single-molecule magnet behavior in the absence of a dc field. In addition, the mononuclear Dy and Tb complexes [{(thf) 2 Li(NtBu) 2 S(tBuN) 2 LnCl 2 (thf) 2 ] (2b,c) show slow magnetic relaxation under applied dc fields.

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Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical

Legendre

¹

,

Stückl

²

,

Sindlinger

³

et al. 2022

Angewandte Chemie

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The reaction of potassium metal with sulfurtriimide S(N t Bu) 3 (II) gives the long elusive deep blue cage radical [K 3 {(N t Bu) 3 S} 2 ] * (1_K) that crystallizes at À 35 °C from toluene solution. The subsequent physical characterization via X-ray structure analysis, UV/Vis-, and EPR spectroscopy from solution reveals the existence of one unpaired electron delocalized within the whole cage, i.e. coupling with the six nitrogen atoms, as well as the three potassium atoms caped by the two SN 3 ligands. The present X-ray structure analysis further supports previous assumptions made on the parent compound 1_Li obtained from [Li 4 {(N t Bu) 3 S} 2 ] (I) and finally elucidates the structural arrangement of the SN 3 caps and alkali metals in such radical cage species.

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Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical

Legendre

¹

,

Stückl

²

,

Sindlinger

³

et al. 2022

Self Cite

View full text Add to dashboard Cite

The reaction of potassium metal with sulfurtriimide S(N t Bu) 3 (II) gives the long elusive deep blue cage radical [K 3 {(N t Bu) 3 S} 2 ] * (1_K) that crystallizes at À 35 °C from toluene solution. The subsequent physical characterization via X-ray structure analysis, UV/Vis-, and EPR spectroscopy from solution reveals the existence of one unpaired electron delocalized within the whole cage, i.e. coupling with the six nitrogen atoms, as well as the three potassium atoms caped by the two SN 3 ligands. The present X-ray structure analysis further supports previous assumptions made on the parent compound 1_Li obtained from [Li 4 {(N t Bu) 3 S} 2 ] (I) and finally elucidates the structural arrangement of the SN 3 caps and alkali metals in such radical cage species.

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Tetraimidoschwefelsäure H₂S(NtBu)₄– isovalenzelektronisch zu H₂SO₄

Cited by 7 publications

References 51 publications

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical

Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical

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Tetraimidoschwefelsäure H2S(NtBu)4– isovalenzelektronisch zu H2SO4

Cited by 7 publications

References 51 publications

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)42− Complexes

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)42− Complexes

Isolation and Properties of the Long Elusive Deep Blue Soluble [K3{(NtBu)3S}2]. Cage Radical

Isolation and Properties of the Long Elusive Deep Blue Soluble [K3{(NtBu)3S}2]. Cage Radical

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Product

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Tetraimidoschwefelsäure H₂S(NtBu)₄– isovalenzelektronisch zu H₂SO₄

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Slow Magnetic Relaxation in Mono‐ and Bimetallic Lanthanide Tetraimido‐Sulfate S(NtBu)₄²⁻ Complexes

Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical

Isolation and Properties of the Long Elusive Deep Blue Soluble [K₃{(N^tBu)₃S}₂]^. Cage Radical