Lanthanide Complexes with a Tripodal Nitroxyl Radical Showing Strong Magnetic Coupling

17 August 2020, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


A series of isomorphous mononuclear complexes of Ln(III) ions comprising one stable tripoidal oxazolidine nitroxyl radical were obtained in acetonitrile media starting from nitrates. The compounds, [LnRad(NO3)3] (Ln = Gd, Tb, Dy, Tm, Y; Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl), have molecular structure. Their coordination polyhedron, LnO7N2, can be described as a tricapped trigonal prism with symmetry close to D3h. The value of 23 cm-1 for the antiferromagnetic coupling Gd-Rad established from the DC magnetic and EPR data is a record strength for the complexes of 4f-elements with nitroxyl radicals. The terbium derivative displays frequency-dependent out-of-phase signals in zero field indicating single-molecule magnetic behavior with an effective barrier of 57 cm-1.


organic radical
oxazolidine nitroxyl radical
heterospin systems
magnetic properties
molecular magnetism
SMM molecules
strong magnetic coupling


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