Coordination Complexes of 1-(4-[<i>N</i>-<i>tert</i>-Butyl-<i>N</i>-aminoxyl]phenyl)-<i>1H</i>-1,2,4-triazole with Paramagnetic Transition Metal Dications

1-(4-(N-tert-Butyl-N-aminoxylphenyl))-1H-1,2,4-triazole (NIT-Ph-Triaz) forms isostructural cyclic 2:2 dimeric complexes with M(hfac)2, M = Mn, Ni, Co, hfac = hexafluoroacetylacetonate. For M = Cu, only a sufficient sample for crystallographic analysis was isolated. For M = Mn, Ni, and Co, the M−NIT exchange is strongly antiferromagnetic. The intradimer exchange coupling between M−NIT units is J/k = +0.53 K for M = Mn, J/k = (−)3.5 K for M = Ni. For M = Co, J/k < 0 K, with the magnetic susceptibility tending toward zero at low temperatures. The exchange behavior is consistent with an intradimer spin polarization mechanism linking M−NIT units through the conjugated π-system of the radical. Computational modeling of NIT-Ph-Triaz gives Mulliken spin populations in good accord with experimental electron spin resonance hyperfine coupling constants, and is consistent with the presumed radical spin density distribution in the complexes. The results provide useful guidelines to anticipate spin polarization effects in organic π-radical building blocks in magnetic materials, particularly when qualitative connectivity-based analyses are clouded by nonalternant molecular connectivities.