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.