Adamantyl-Substituted Aminoxyls.

The interaction of perfluoroaromatic compounds with 1-aminoadamantane followed by oxidation of the formed N-adamantylanilines with meta-chloroperoxybenzoic acid led to functionalized N-polyfluorophenyl-N-adamantylaminoxyls (mono- and diradicals) in high total yields. The molecular and crystal structures of N-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 N-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.