New members of radical bridged Ln₂ metallocene single-molecule magnets based on the unsubstituted 1,2,4,5-tetrazine ligand
Mavragani, Niki; Kitos, Alexandros A.; Mansikkamäki, Akseli; Murugesu, Muralee (2022-11-22)
Mavragani, N., Kitos, A. A., Mansikkamäki, A., & Murugesu, M. (2023). New members of radical bridged Ln 2 metallocene single-molecule magnets based on the unsubstituted 1,2,4,5-tetrazine ligand. Inorganic Chemistry Frontiers, 10(1), 259–266. https://doi.org/10.1039/D2QI02164A
© 2023 The Royal Society of Chemistry. The final authenticated version is available online at https://doi.org/10.1039/D2QI02164A.
https://rightsstatements.org/vocab/InC/1.0/
https://urn.fi/URN:NBN:fi-fe202301276206
Tiivistelmä
Abstract
Magnetic coupling plays a critical role in the overall magnetic behaviour of a single-molecule magnet (SMM). Through a careful design strategy that employs the highly delocalized 1,2,4,5-tetrazinyl (tz) radical anion with lanthanide metallocenes, a new family of dinuclear complexes was isolated; [(Cp*₂LnIII)₂(tz˙−)(THF)₂](BPh₄), (Ln = Gd (1), Tb (2), Dy (3); THF = tetrahydrofuran; Cp* = pentamethylcyclopentadienyl). The strong magnetic exchange coupling of JGd–rad = −7.2 cm−1 observed in 1, was probed through SQUID magnetometry as well as computational studies. This, combined with the highly anisotropic TbIII and DyIII ions in 2 and 3, respectively, leads to zero-field SMM behaviour and slow relaxation of the magnetization through thermally activated processes. These dinuclear complexes serve as ideal models for understanding the magnetic interactions between 4f elements
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