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.