Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets

Based on the potassium [{S(tBuN)(2)(tBuNH)}(2)K(3)(tmeda)‐K(3){(HNtBu)(NtBu)(2)S}(2)] (1) and sodium precursors [S(tBuN)(3)(thf)(3)‐Na(3)SNa(3)(thf)(3)(NtBu)(3)S] (2), [S(tBuN)(3)(thf)(3)Na(3){(HNtBu)(NtBu)(2)S}] (3) and [(tmeda)(3)S‐{Na(3)(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 Dy(III)‐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.