Andrew J. Valentine
Slow magnetic relaxation in Fe(ii) m-terphenyl complexes
Valentine, Andrew J.; Geer, Ana M.; Blundell, Toby J.; Tovey, Will; Cliffe, Matthew J.; Davies, E. Stephen; Argent, Stephen P.; Lewis, William; McMaster, Jonathan; Taylor, Laurence J.; Reta, Daniel; Kays, Deborah L.
Authors
Ana M. Geer
Toby J. Blundell
Will Tovey
MATTHEW CLIFFE Matthew.Cliffe@nottingham.ac.uk
Associate Professor
E. Stephen Davies
STEPHEN ARGENT stephen.argent@nottingham.ac.uk
Senior Research Fellow
William Lewis
JONATHAN MCMASTER Jonathan.McMaster@nottingham.ac.uk
Professor of Chemistry
LAURENCE TAYLOR Laurence.Taylor@nottingham.ac.uk
Teaching Associate in Organic Chemistry
Daniel Reta
DEBORAH KAYS DEBORAH.KAYS@NOTTINGHAM.AC.UK
Professor of Inorganic Chemistry
Abstract
Two-coordinate transition metal complexes are exciting candidates for single-molecule magnets (SMMs) because their highly axial coordination environments lead to sizeable magnetic anisotropy. We report a series of five structurally related two-coordinate Fe(ii) m-terphenyl complexes (4-R-2,6-Xyl2C6H2)2Fe [R = tBu (1), SiMe3 (2), H (3), Cl (4), CF3 (5)] where, by changing the functionalisation of the para-substituent (R), we alter their magnetic function. All five complexes are field-induced single-molecule magnets, with relaxation rates that are well-described by a combination of direct and Raman mechanisms. By using more electron donating R groups we were able to slow the rate of magnetic relaxation. Our ab initio calculations predict a large crystal field splitting (>850 cm−1) and sizeable zero-field splitting parameters (ca. −60 cm−1, |E| < 0.2 cm−1) for 1-5. These favourable magnetic properties suggest that m-terphenyl ligands have untapped potential as chemically versatile ligands able to impose highly axial crystal fields.
Journal Article Type | Article |
---|---|
Acceptance Date | Nov 7, 2022 |
Online Publication Date | Nov 8, 2022 |
Publication Date | Dec 21, 2022 |
Deposit Date | Dec 1, 2022 |
Publicly Available Date | Dec 1, 2022 |
Journal | Dalton Transactions |
Print ISSN | 1477-9226 |
Electronic ISSN | 1477-9234 |
Publisher | Royal Society of Chemistry (RSC) |
Peer Reviewed | Peer Reviewed |
Volume | 51 |
Issue | 47 |
Pages | 18118-18126 |
DOI | https://doi.org/10.1039/d2dt03531f |
Keywords | Inorganic Chemistry |
Public URL | https://nottingham-repository.worktribe.com/output/13754716 |
Publisher URL | https://pubs.rsc.org/en/content/articlelanding/2022/DT/D2DT03531F |
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Publisher Licence URL
https://creativecommons.org/licenses/by/3.0/
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