Exploring through-bond and through-space magnetic communication in 1,3,2-dithiazolyl radical complexes

Reaction of the methyl-benzodithiazolyl radical (MBDTA) with M(hfac)2 complexes (M = Mn, Co, Zn) affords the complexes M(hfac)2(MBDTA)2. Strong antiferromagnetic exchange interactions are observed between M(II) ions and the two S = ½ radicals (M = Mn, Co), whereas weak antiferromagnetic interactions are observed between radicals when using the diamagnetic Zn(II) ion. Strong intermolecular exchange coupling is also evident in Mn(hfac)2(MBDTA)2 and attributed to π*-π* contacts between MBDTA radicals which are absent for the Co and Zn derivatives.