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)

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: Wilson, Dr Claire and Tsanai, Dr Angelos and Regincos Marti, Miss Emma and Murrie, Professor Mark
• 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

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
69698	1	Putting the Squeeze on Molecule-Based Magnets	Mark Murrie	Engineering and Physical Sciences Research Council (EPSRC)	EP/N01331X/1	CHEM - CHEMISTRY