Single-Ion Magnetic Behavior in CoII-CoIII Mixed-Valence Dinuclear and Pseudodinuclear Complexes

Two CoII–CoIII mixed-valence complexes of molecularformulas [Co2(H2L)2(H2O)2][Co2(H2L)2(H2O)(m-phth)]·8(H2O) {1;H2L2–= 2-[(2-hydroxy-3-methoxybenzylidene)amino]-2-(hydroxymethyl)propane-1,3-diolato, m-phth = 1,3-benzene-dicarboxylate} and [Co4(H2L)4(H2O)2(ppda)]·2(dmf)·3.2(H2O) {2;ppda = 1,4-phenylenediacrylate; dmf = N,N-dimethyl-formamide} were synthesized and characterized by single-crys-tal X-ray diffraction and magnetic studies at low temperature.The structural determination reveals that 1 is composed of di-nuclear ion pairs, namely, a cationic [Co2(H2L)2(H2O)2]+(1+) andan anionic [Co2(H2L)2(H2O)(m-phth)]–(1–) unit. In each of these ions, the CoIIand CoIIIcenters present distorted octahedralgeometries. Compound 2 is a centrosymmetric tetranuclearcomplex comprising two symmetry-related dinuclear CoII–CoIIIunits bridged by ppda anions.