Insight into D 6 h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single‐Ion Magnets
| Autor: | Sourav Dey, Angelos B. Canaj, Claire Wilson, Mark Murrie, Emma Regincós Martí, Gopalan Rajaraman |
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| Rok vydání: | 2019 |
| Předmět: |
Ligand field theory
Materials science chemistry.chemical_element 010402 general chemistry 01 natural sciences Catalysis Ion single molecule magnets hexagonal bipyramid Ab initio quantum chemistry methods Single‐Molecule Magnets dysprosium Anisotropy Hexagonal bipyramid 010405 organic chemistry Communication ab initio calculations General Chemistry General Medicine Communications 0104 chemical sciences 3. Good health Crystallography Bipyramid Magnetic anisotropy chemistry Dysprosium magnetic properties |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1521-3757 0044-8249 |
| Popis: | Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph3SiO− (Ph3SiO−=anion of triphenylsilanol) and the 2,4‐di‐tBu‐PhO− (2,4‐di‐tBu‐PhO−=anion of 2,4‐di‐tertbutylphenol) ligands combined with the weak equatorial field of the ligand LN6, leads to [DyIII(LN6)(2,4‐di‐tBu‐PhO)2](PF6) (1), [DyIII(LN6)(Ph3SiO)2](PF6) (2) and [DyIII(LN6)(Ph3SiO)2](BPh4) (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. Combining a strong linear axial ligand field with a weak equatorial ligand field, by using the polydentate ligand LN6, reveals for the first time the exceptional uniaxial magnetic anisotropy possible for D 6h symmetry. This opens up a route to further air‐stable higher‐order symmetry single‐molecule magnets. |
| Databáze: | OpenAIRE |
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