Abstract
Two diradical complexes of the formula [LnRad2(CF3SO3)3] c (Ln(III) = Dy, Eu, Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl) were obtained in air conditions. These are the first examples of diradical compounds of lanthanides and oxazolidine nitroxide. The complexes were characterized crystallographically and magnetically. Single crystal XRD analysis revealed that their coordination sphere is composed of three monodentate triflates and two tripodal Rad, which coordinate the central atom in a tridentate manner via two N atoms of the pyridine groups and the O atom of a nitroxide group. The LnO5N4 polyhedron represents a spherical capped square antiprism with point symmetry close to C4v. The data of static magnetic measurements are compatible with the presence of two paramagnetic ligands in the coordination sphere of the metal.
Highlights
The study of single-molecule magnets (SMMs) is the most intensively developing area of molecular magnetism
These molecules exhibit bulk magnet-like property-magnetic hysteresis, and their nanosize nature leads to quantum tunnelling of the magnetization (QTM)
The reaction of a dichloromethane solution containing the stoichiometric amounts of Dy(CF3SO3)3 and 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl (Rad) (Scheme 1) at 40 âŠC afforded the diradical complex [DyRad2(CF3SO3)3] (1)
Summary
The study of single-molecule magnets (SMMs) is the most intensively developing area of molecular magnetism. Strong axial anisotropy can be enforced by an appropriate design of the crystal field splitting (CFS) [13,16,17,18], and the provision of large enough energy splitting on the Ln sites is required to reduce the QTM between ground states. For this reason, it is very important to study minor changes in ligand-field strength associated with the coordination polyhedrons of the LnIII complexes. It is hard to implement systematic control of the coordination geometries and the ligand-field strength of LnIII compounds [19]
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