Synthesis, Structure and Magnetic Differences of Two a-Nitronyl Nitroxide Isomers


  • Araceli Vega Universidad Autónoma Metropolitana Iztapalapa
  • Juan Padilla Universidad Autónoma Metropolitana Iztapalapa
  • Marco Antonio Leyva Centro de Investigaciones y Estudios Avanzados
  • María del Jesús Rosales Centro de Investigaciones y Estudios Avanzados
  • Sylvain Bernès UANL



organic radicals, isomers, nitronyl nitroxides, ferromagnetism, antiferromagnetism, phase transition, structure


The two isomeric organic nitronyl nitroxide free radicals 2-(2’-hydroxyl-3’-methoxy-phenyl)-4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazoyl-1-oxyl-3-oxide, 1, and 2-(3’-hydroxyl-4’-methoxyphenyl)-4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazoyl-1-oxyl-3-oxide, 2, have been synthesized and their structures determined by X-ray diffraction. Structure 1 has three dimensional, strong, intramolecular hydrogen bonds in addition to intermolecular interactions favoring sheets. The structure of radical 2 also shows strong hydrogen bonds both intra- and intermolecular. Some of these bonds are with a lattice water molecule, yielding a three-dimensional crystal structure. An important structural difference between both radicals is that in compound 1, one of the nitrogen atoms of the radical shows smaller angles than the other atom in the same radical and than both nitrogen atoms in compound 2. This suggests that in 1, one of the nitrogen atoms has a higher sp3 character than the other. This proposal is supported by the N-O bond length which is significantly longer in the spnitrogen side. Both isomers show quite different magnetic behavior. In 1 there are both ferromagnetic (JF/k = + 0.11 ± 0.01 K) and antiferromagnetic (JAF/k = - 0.81 ± 0.10 K) interactions, whereas 2 only shows antiferromagnetism (JAF/k = - 1.60 ± 0.02 K) with a phase transition at Tc = 2.48 K.




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Author Biographies

Araceli Vega, Universidad Autónoma Metropolitana Iztapalapa

Departamento de Química

Juan Padilla, Universidad Autónoma Metropolitana Iztapalapa

Departamento de Química

Marco Antonio Leyva, Centro de Investigaciones y Estudios Avanzados

Departamento de Química

María del Jesús Rosales, Centro de Investigaciones y Estudios Avanzados

Departamento de Química

Sylvain Bernès, UANL

DEP, Facultad de Ciencias Químicas


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