Strong Magnetic Coupling and Single‐Molecule Magnet Behavior in Tetrazinyl Radical‐Bridged Metallocenes
Exchange coupling is essential in defining the magnetic behavior of polymetallic lanthanide-based (Ln<sup>III</sup>) single-molecule magnets (SMMs), where, thanks to the unpaired electron(s), radical ligands show promise as magnetic bridges between the paramagnetic metal centers. Combining high-performance lanthanide metallocene [Cp*₂Ln]<sup>+</sup> (Cp* = pentamethylcyclopentadienyl) units with the 3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine radical ligand (bmtz<sup>•-</sup>) yielded two new radical-bridged dinuclear lanthanide metallocenes, [(Cp*₂Ln)₂(bmtz<sup>•-</sup>)](BPh<sub>4</sub>)·Solvent (Ln = Gd (1), Solvent = THF; Dy (2), Solvent = toluene). The strong magnetic exchange coupling of J<sub>Gd-rad</sub> = -12.6 cm<sup>-1</sup> observed in 1, was probed via SQUID magnetometry as well as computational studies. This, combined with the highly anisotropic Dy<sup>III</sup> ions in 2, leads to zero-field SMM behavior and slow magnetic relaxation through thermally activated processes.
Authors
- Rezeda Gayfullina (ORCID: https://orcid.org/0000-0001-6023-9804)
- Alexandros A. Kitos (ORCID: https://orcid.org/0000-0002-1431-3206)
- Jani O. Moilanen (ORCID: https://orcid.org/0000-0002-2096-593X)
- Niki Mavragani (ORCID: https://orcid.org/0000-0003-0069-3233)
- Muralee Murugesu (ORCID: https://orcid.org/0000-0002-5123-374X)
- Neha Bajaj (ORCID: https://orcid.org/0009-0001-0487-3656)
Institutions
- University of Ottawa (CA)
- University of Jyväskylä (FI)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-07-01
- DOI
- https://doi.org/10.1002/chem.202501542
- Citations
- 3
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 1.28
Funders
- University of Ottawa
- Canada Foundation for Innovation
- Stavros Niarchos Foundation
- China Scholarship Council
- Jyväskylän Yliopisto
- Oulun Yliopisto
- Natural Sciences and Engineering Research Council of Canada