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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.

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Authors

Andrew J. Valentine

Ana M. Geer

Toby J. Blundell

Will Tovey

E. Stephen Davies

William Lewis

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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.

Citation

Valentine, A. J., Geer, A. M., Blundell, T. J., Tovey, W., Cliffe, M. J., Davies, E. S., …Kays, D. L. (2022). Slow magnetic relaxation in Fe(ii) m-terphenyl complexes. Dalton Transactions, 51(47), 18118-18126. https://doi.org/10.1039/d2dt03531f

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 Mar 28, 2024
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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