A Spontaneous Magnetic Moment in an Organic Radical: Synthesis and Characterization of Benzodioxepinyl-1,3,2-dithiazolyl.

Autor: Leckie D; Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada., Harb M; Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada., Mroz N; Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada., Wrixon JD; Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada., Campo J; Instituto de Nanociencia y Materiales de Aragón (CSIC-University of Zaragoza) and Physics Condensed Matter Department, Facultad de Ciencias, C/Pedro Cerbuna 12, Zaragoza E-50009 Spain., Arauzo A; Instituto de Nanociencia y Materiales de Aragón (CSIC-University of Zaragoza) and Physics Condensed Matter Department, Facultad de Ciencias, C/Pedro Cerbuna 12, Zaragoza E-50009 Spain., Bakhshi H; Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St Catharines, ON L2S 3A1, Canada., Pilkington M; Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St Catharines, ON L2S 3A1, Canada., Rawson JM; Department of Chemistry & Biochemistry, University of Windsor, 401 Sunset Avenue, Windsor, ON N9B 3P4, Canada.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Nov 20; Vol. 146 (46), pp. 31371-31376. Date of Electronic Publication: 2024 Nov 07.
DOI: 10.1021/jacs.4c09796
Abstrakt: 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 (T N = 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.
Databáze: MEDLINE