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Alkali Metal Based Triimidosulfite Cages as Versatile Precursors for Single‐Molecule Magnets
Author(s) -
Lüert Daniel,
Legendre Christina M.,
HerbstIrmer Regine,
Stalke Dietmar
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202104470
Subject(s) - alkali metal , lanthanide , chemistry , potassium , lithium (medication) , sodium , crystallography , relaxation (psychology) , metal , magnetization , inorganic chemistry , ion , organic chemistry , magnetic field , physics , medicine , social psychology , psychology , endocrinology , quantum mechanics
Based on the potassium [{S( t BuN) 2 ( t BuNH)} 2 K 3 (tmeda)‐K 3 {(HN t Bu)(N t Bu) 2 S} 2 ] ( 1 ) and sodium precursors [S( t BuN) 3 (thf) 3 ‐Na 3 SNa 3 (thf) 3 (N t Bu) 3 S] ( 2 ), [S( t BuN) 3 (thf) 3 Na 3 {(HN t Bu)(N t Bu) 2 S}] ( 3 ) and [(tmeda) 3 S‐{Na 3 (N t Bu) 3 S} 2 ] ( 4 ) the syntheses and magnetic properties of three mixed metal triimidosulfite based alkali‐lanthanide‐metal‐cages [( t BuNH)Dy{K(0.5tmeda)} 2 {(N t Bu) 3 S} 2 ] n ( 5 ) and [ClLn{Na(thf)} 2 {(N t Bu) 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.