This paper gives a brief overview of a new approach to chalcogen-nitrogen heterocyclic π-radicals, particularly 1,2,3- and 1,3,2-benzodithiazolyls, based on thermolysis or photolysis of closed-shell precursors (such as 1,3,2,4-benzodithiadiazines and their 1-Se congeners, 1,2,4,3,5- and 1,3,5,2,4-benzotrithiadiazepines, and some other sulfur-nitrogen rings and cages). The approach allows obtaining radicals hardly accessible or inaccessible in other ways, especially, fluorinated radicals. The identity of radicals prepared is confirmed by electron paramagnetic resonance spectroscopy in combination with density functional theory calculations.
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