A Spontaneous Magnetic Moment in an Organic Radical: Synthesis and Characterization of
Dominique Leckie1, Mohamad Harb1, Natalia Mroz1
1Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada.
Abstract:
The synthesis of the 1,3,2-dithiazolyl radical (1) derived from 3,4-dihydro-2H-1,5-benzodioxepine is described. Crystals of 1 were grown by vacuum sublimation and adopt the orthorhombic space group Pbca. DC SQUID magnetometry reveals Curie-Weiss behavior for T > 20 K (C = 0.376 emu K mol-1 and θ = +5.7 K) consistent with local ferromagnetic interactions. The presence of weaker antiferromagnetic interactions led to magnetic ordering as a canted antiferromagnet (TN = 3.8 K) with a small spontaneous moment (2.5 × 10-4 Nβ) and a small coercivity (ca. 8 Oe) at 2 K. Magnetic ordering was reflected in a field dependence of the magnetic susceptibility below 3.8 K and a peak in the low temperature heat capacity data. A canting angle of 0.08° was estimated from M vs H data.
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