Adamantyl-Substituted Aminoxyls

The interaction of perfluoroaromatic compounds with 1-aminoadamantane followed by oxidation of the formed <i>N</i>-adamantylanilines with <i>meta</i>-chloroperoxybenzoic acid led to functionalized <i>N</i>-polyfluorophenyl-<i>N</i>-adamantylaminoxyls (mono- and diradicals) in high total yields. The molecular and crystal structures of <i>N</i>-adamantylanilines and the aminoxyl radicals obtained from them by oxidation have been established using single-crystal X-ray diffraction analysis. The introduction of a substituent into the polyfluorinated moiety affects the arrangement of <i>N</i>-adamantylanilines in the crystal structure and the formation of hydrogen bonds; in addition, short contacts of the rare N···N type are present in crystals of 4-((adamantan-1-yl)amino)-perfluorobiphenyl. In crystals of the aminoxyls, oxygen atoms make unusually short contacts with C atoms of polyfluorinated aromatic rings giving rise to ferromagnetic exchange.