Slow magnetic relaxation at zero field in the tetrahedral complex [Co(SPh)4]2-

The Ph(4)P(+) salt of the tetrahedral complex Co(SPh)(4)](2-), possessing an S = (3)/(2) ground state with an axial zero-field splitting of D = -70 cm(-1), displays single-molecule magnet behavior in the absence of an applied magnetic field. At very low temperatures, ac magnetic susceptibility data show the magnetic relaxation time, τ, to be temperature-independent, while above 2.5 K thermally activated Arrhenius behavior is apparent with U(eff) = 21(1) cm(-1) and τ(0) = 1.0(3) × 10(-7) s. Under an applied field of 1 kOe, τ more closely approximates Arrhenius behavior over the entire temperature range. Upon dilution of the complex within a matrix of the isomorphous compound (Ph(4)P)(2)Zn(SPh)(4)], ac susceptibility data reveal the molecular nature of the slow magnetic relaxation and indicate that the quantum tunneling pathway observed at low temperatures is likely mediated by intermolecular dipolar interactions.