화학공학소재연구정보센터
Inorganic Chemistry, Vol.44, No.3, 649-653, 2005
Inelastic neutron scattering study of electron reduction in Mn-12 derivatives
We report inelastic neutron scattering (INS) studies on a series of Mn-12 derivatives, [Mn12O12(O2CC6F5)(16)(H2O)(4)](Z), in which the number of unpaired electrons in the cluster is varied. We investigated three oxidation levels: z = 0 for the neutral complex, z = -1 for the one-electron reduced species and z = -2 for the two-electron reduced complex. For z = 0, the ground state is S = 10 as in the prototypical Mn-12-acetate. For z = -1, we have S = 19/2, and for z = -2, an S = 10 ground state is retrieved. INS studies show that the axial zero-field splitting parameter D is strongly suppressed upon successive electron reduction: D = -0.45 cm(-1) (z = 0), D = -0.35 cm(-1) (z = -1), and D approximate to -0.26 cm(-1) (z = -2). Each electron reduction step is directly correlated to the conversion of one anisotropic (Jahn-Teller distorted) Mn3+ (S = 2) to one nearly isotropic Mn2+ (S = 5/2).