Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of CoII-based single-ion magnets. Using multi-frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five-coordinate CoII complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their CoII complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane CoII complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.

Rotaxane CoII Complexes as Field-Induced Single-Ion Magnets

Salvadori E.;
2021

Abstract

Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of CoII-based single-ion magnets. Using multi-frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five-coordinate CoII complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their CoII complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane CoII complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.
ANGEWANDTE CHEMIE. INTERNATIONAL EDITION
60
29
16051
16058
https://onlinelibrary.wiley.com/doi/full/10.1002/anie.202103596
electron paramagnetic resonance; magnetism; rotaxanes; single ion magnets; zero-field splitting
Cirulli M.; Salvadori E.; Zhang Z.-H.; Dommett M.; Tuna F.; Bamberger H.; Lewis J.E.M.; Kaur A.; Tizzard G.J.; van Slageren J.; Crespo-Otero R.; Goldup S.M.; Roessler M.M.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/1837524
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