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Recent developments in the chemistry of stable chalcogen–nitrogen radicals are discussed, with an emphasis on their electronic structure and bulk physical properties of these radicals and their metal complexes. The strength of radical–radical magnetic interactions gives rise to long‐range magnetic order (ferromagnetism, antiferromagnetism, canted antiferromagnetism) at high temperatures (T <70 K). Chalcogen–nitrogen radicals which span the spectrum from insulating through semiconducting to conducting behaviour are described.

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