Assembly of Imidazolyl-Substituted Nitronyl Nitroxides into Ferromagnetically Coupled Chains

Abstract

New nitronyl nitroxides, namely, 2-(4,5-dimethylimidazol-2-yl)- and 2-(4,5-dichloroimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl, were prepared in crystalline form. According to single-crystal X-ray data, intra- and intermolecular hydrogen bonds are formed between NH groups of the imidazole cycles and O atoms of the nitroxide moieties. The intermolecular H-bonds contribute to the alignment of molecules into chains along the a-axis; this alignment causes short intrachain contacts between O and C atoms carrying spin density of opposite signs. Such an arrangement of nitroxides induces ferromagnetic intrachain interactions (J ≈ 10 cm−1) between neighboring radicals.

Keywords

• nitronyl nitroxides
• imidazole
• crystal structure
• hydrogen bonding
• exchange interaction
• density functional theory