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Updated: Oct 6, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single-Molecule Magnets
Daniel Lüert1, Christina M Legendre1, Regine Herbst-Irmer1
1Institut für Anorganische Chemie, Georg-August-University Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.
Abstract:
Based on the potassium [{S(tBuN)2 (tBuNH)}2 K3 (tmeda)-K3 {(HNtBu)(NtBu)2 S}2 ] (1) and sodium precursors [S(tBuN)3 (thf)3 -Na3 SNa3 (thf)3 (NtBu)3 S] (2), [S(tBuN)3 (thf)3 Na3 {(HNtBu)(NtBu)2 S}] (3) and [(tmeda)3 S-{Na3 (NtBu)3 S}2 ] (4) the syntheses and magnetic properties of three mixed metal triimidosulfite based alkali-lanthanide-metal-cages [(tBuNH)Dy{K(0.5tmeda)}2 {(NtBu)3 S}2 ]n (5) and [ClLn{Na(thf)}2 {(NtBu)3 S}2 ] with Ln=Dy (6), Er (7) are reported. The corresponding potassium (1) and sodium (2-4) based cages are characterized through XRD and NMR experiments. Preventing lithium chloride co-complexation led to a significant increase of SMM performance to previously reported sulfur-nitrogen ligands. The subsequent DyIII -complexes 5 and 6 display slow relaxation of magnetization at zero field, with relaxation barriers U=77.0 cm-1 for 5, 512.9 and 316.3 cm-1 for 6, respectively. Significantly, the latter complex 6 also exhibits a butterfly-shaped hysteresis up to 7 K.
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