Insight into D6h symmetry: targeting strong axiality in stable dysprosium(III) hexagonal bipyramidal single-ion magnets

Canaj, A. B. , Dey, S., Regincós Marti, E., Wilson, C. , Rajaraman, G. and Murrie, M. (2019) Insight into D6h symmetry: targeting strong axiality in stable dysprosium(III) hexagonal bipyramidal single-ion magnets. Angewandte Chemie (International Edition), 58(40), pp. 14146-14151. (doi: 10.1002/anie.201907686) (PMID:31343095) (PMCID:PMC6790654)

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Abstract

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 Ueff=973 K for 1, Ueff=1080 K for 2 and Ueff=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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Murrie, Professor Mark and Wilson, Dr Claire and Tsanai, Dr Angelos and Regincós Martí, Emma
Authors: Canaj, A. B., Dey, S., Regincós Marti, E., Wilson, C., Rajaraman, G., and Murrie, M.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
Publisher:Wiley
ISSN:1433-7851
ISSN (Online):1521-3773
Published Online:25 July 2019
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Angewandte Chemie (International Edition) 58(40): 14146-14151
Publisher Policy:Reproduced under a Creative Commons license

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
696981Putting the Squeeze on Molecule-Based MagnetsMark MurrieEngineering and Physical Sciences Research Council (EPSRC)EP/N01331X/1CHEM - CHEMISTRY