Radical-Bridged Ln4 Metallocene Complexes with Strong Magnetic Coupling and a Large Coercive Field.
Niki MavraganiDylan ErrulatDiogo A GálicoAlexandros A KitosAkseli MansikkamäkiMuralee MurugesuPublished in: Angewandte Chemie (International ed. in English) (2021)
Inducing magnetic coupling between 4f elements is an ongoing challenge. To overcome this formidable difficulty, we incorporate highly delocalized tetrazinyl radicals, which strongly couple with f-block metallocenes to form discrete tetranuclear complexes. Synthesis, structure, and magnetic properties of two tetranuclear [(Cp*2 Ln)4 (tz. )4 ]⋅3(C6 H6 ) (Cp*=pentamethylcyclopentadienyl; tz=1,2,4,5-tetrazine; Ln=Dy, Gd) complexes are reported. An in-depth examination of their magnetic properties through magnetic susceptibility measurements as well as computational studies support a highly sought-after radical-induced "giant-spin" model. Strong exchange interactions between the LnIII ions and tz. radicals lead to a strong magnet-like behaviour in this molecular magnet with a large coercive field of 30 kOe.