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CSIRO Publishing, Australian Journal of Chemistry, 11(67), p. 1618, 2014

DOI: 10.1071/ch14390

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Manganese(II) Oxazolidine Nitroxide Chelates: Structure, Magnetism, and Redox Properties

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

The mononuclear oxazolidine nitroxide complex [MnII(L•)2](ClO4)2 (1) (L•, 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide) has been synthesized and investigated using single-crystal X-ray diffraction, variable-temperature magnetic susceptibility measurements, and electrochemistry. The structural analysis reveals bond lengths compatible with a linear L•–MnII–L• arrangement where the ligands are in the neutral ligand form and the central MnII ion is high spin (S = 5/2). Although analysis of the variable-temperature magnetic susceptibility data suggests a strong antiferromagnetic metal–radical interaction, the radical–radical intramolecular interaction could not be determined unambiguously from such fits. The resultant isolated S = 3/2 ground state is confirmed by low-temperature magnetization versus field measurements. Electrochemical studies reveal similar square schemes and redox intermediates to the previously reported analogues [FeII(L•)2][BF4]2 and [CoII(L•)2][NO3]2.

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