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Rotaxane CoII Complexes as Field-Induced Single-Ion Magnets

preprint
submitted on 17.03.2021, 15:08 and posted on 18.03.2021, 12:56 by Martina Cirulli, Enrico Salvadori, Zhi-Hui Zhang, Michael Dommett, Floriana Tuna, Heiko Bamberger, James Lewis, Amanpreet Kaur, Graham Tizzard, Joris van Slageren, Rachel Crespo Otero, Stephen Goldup, Maxie Roessler
Mechanically chelating ligands have untapped potential for the engineering of metal ion properties by providing reliable control of the number, nature and geometry of donor atoms, akin to how a protein cavity controls the properties of bound metal ions. 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 behavior 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 behavior of the rotaxane CoII complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.

Funding

Click to Lock: Mechanically Interlocked Architectures as Hydrogen Evolving Catalysts

European Commission

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Mechanical Chirality: Synthesis, Properties and Applications at a New Horizon in Supramolecular Stereochemistry

European Research Council

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Towards the Computational Design of Highly Emissive Organic-Single Crystals

Engineering and Physical Sciences Research Council

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History

Email Address of Submitting Author

s.goldup@soton.ac.uk

Institution

UNIVERSITY OF SOUTHAMPTON

Country

United Kingdom

ORCID For Submitting Author

0000-0003-3781-0464

Declaration of Conflict of Interest

None

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