Manganese(II) Oxazolidine Nitroxide Chelates: Structure, Magnetism, and Redox Properties
AUSTRALIAN JOURNAL OF CHEMISTRY(2014)
Abstract
The mononuclear oxazolidine nitroxide complex [Mn-II(L-center dot)(2)](ClO4)(2) (1) (L-center dot, 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-center dot-Mn-II-L-center dot arrangement where the ligands are in the neutral ligand form and the central Mn-II 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 [Fe-II(L-center dot)(2)][BF4](2) and [Co-II(L-center dot)(2)][NO3](2).
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