Strong magnetic exchange coupling in Ln2 metallocenes attained by the trans-coordination of a tetrazinyl radical ligand
Mavragani, N., Kitos, A. A., Hrubý, J., Hill, S., Mansikkamäki, A., Moilanen, J. O., & Murugesu, M. (2023). Strong magnetic exchange coupling in Ln2 metallocenes attained by the trans-coordination of a tetrazinyl radical ligand. Inorganic Chemistry Frontiers, 10(14), 4197-4208. https://doi.org/10.1039/d3qi00290j
Julkaistu sarjassa
Inorganic Chemistry FrontiersTekijät
Päivämäärä
2023Oppiaine
Epäorgaaninen ja analyyttinen kemiaNanoscience CenterEpäorgaaninen kemiaInorganic and Analytical ChemistryNanoscience CenterInorganic ChemistryTekijänoikeudet
© the Partner Organisations 2023
A combination of high-performing lanthanide metallocenes and tetrazine-based radical ligands leads to a new series of radical-bridged dinuclear lanthanide metallocenes; [(Cp*2LnIII)2(bpytz˙−)][BPh4] (where Ln = Gd (1), Tb (2), Dy (3) and Y (4); Cp* = pentamethylcyclopentadienyl; bpytz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine). The formation of the radical species is achieved via a controlled, stepwise synthesis and verified in all complexes by X-ray crystallography and SQUID magnetometry, as well as EPR spectroscopy of 4. Through the judicious choice of the Cp* ancillary ligands and by taking advantage of the steric effects imposed by their bulkiness, we were able to promote the trans coordination mode of the bpytz˙− radical anion that enables stronger magnetic exchange coupling compared to the cis fashion. This yields a JGd–rad = −14.0 cm−1 in 1, which is the strongest exchange coupling observed in organic monoanionic radical-bridged lanthanide metallocene systems. The strong Ln-rad exchange coupling was further confirmed by high-frequency EPR (HF-EPR) spectroscopy and broken-symmetry (BS) density functional theory (DFT) calculations. This combined with the highly anisotropic nature of TbIII and DyIII ions in 2 and 3, respectively, leads to strong SMM behavior and slow relaxation of the magnetization at zero fields.
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Julkaisija
Royal Society of Chemistry (RSC)ISSN Hae Julkaisufoorumista
2052-1545Asiasanat
Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/183951862
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Rahoittaja(t)
Suomen AkatemiaRahoitusohjelmat(t)
Akatemiatutkijan tutkimuskulut, SA; Akatemiatutkija, SALisätietoja rahoituksesta
N. M., A. A. K. and M. M. thank the University of Ottawa, the Canada Foundation for Innovation (CFI) and the Natural Sciences and Engineering Research Council of Canada (NSERC) for the financial support of this work. N. M. acknowledges the University of Ottawa and the Stavros Niarchos Foundation for financial support through scholarships. J. H. and S. H. acknowledge support from the US Department of Energy, Basic Energy Sciences (DE-SC0020260). Work performed at the National High Magnetic Field Laboratory is supported by the US National Science Foundation (DMR-1644779) and the State of Florida. A. M. acknowledges funding provided by the Academy of Finland (grant no. 332294) and the University of Oulu (Kvantum Institute). J. O. M. acknowledges the Academy of Finland (projects 315829 and 345484) for the financial support, and the CSC-IT Centre for Science in Finland, the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) and Prof. H. M. Tuononen (University of Jyväskylä) for providing computational resources for the project. ...Lisenssi
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