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Insight into D 6 h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single‐Ion Magnets
Author(s) -
Canaj Angelos B.,
Dey Sourav,
Martí Emma Regincós,
Wilson Claire,
Rajaraman Gopalan,
Murrie Mark
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201907686
Subject(s) - dysprosium , crystallography , chemistry , ligand field theory , magnetic anisotropy , ion , anisotropy , magnetization , trigonal bipyramidal molecular geometry , ab initio quantum chemistry methods , hexagonal crystal system , ligand (biochemistry) , ab initio , molecule , condensed matter physics , magnetic field , crystal structure , inorganic chemistry , physics , biochemistry , receptor , organic chemistry , quantum mechanics
Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph 3 SiO − (Ph 3 SiO − =anion of triphenylsilanol) and the 2,4‐di‐ t Bu‐PhO − (2,4‐di‐ t Bu‐PhO − =anion of 2,4‐di‐ tert butylphenol) ligands combined with the weak equatorial field of the ligand L N6 , leads to [Dy III (L N6 )(2,4‐di‐ t Bu‐PhO) 2 ](PF 6 ) ( 1 ), [Dy III (L N6 )(Ph 3 SiO) 2 ](PF 6 ) ( 2 ) and [Dy III (L N6 )(Ph 3 SiO) 2 ](BPh 4 ) ( 3 ) hexagonal bipyramidal dysprosium(III) single‐molecule magnets (SMMs) with high anisotropy barriers of U eff =973 K for 1 , U eff =1080 K for 2 and U eff =1124 K for 3 under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher‐order symmetry SMMs.