Synthesis, spectroscopic [electron paramagnetic resonance (EPR), UV-Vis and Fourier transform infrared spectroscopy (FTIR)], magnetic and spectroeletrochemical properties of [MnII2(tidf)(OAc)(ClO4)(MeOH)] (tidf = a Robson type macrocyclic ligand obtained through condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane) are reported. Compound [MnII2(tidf)(OAc)(ClO4)(MeOH)] shows a weak antiferromagnetic behavior with exchange coupling constant J = -1.59(1) cm-1. UV-Vis and EPR spectroelectrochemical response after oxidation of complex [MnII2(tidf)(OAc)(ClO4)(MeOH)] detected the stabilization of mixed-valence Mn2(II/III) species in solution showing spectral features similar to the ones of the isolated mixedvalence [MnII MnIII(tidf)Br3(H2O)2] compound. Crystallization of [MnII2(tidf)(OAc)(ClO4)(MeOH)] surprisingly produced the trimanganese complex [Mn3III/II/III(tidf)2(µ-OAc)2](ClO4)2, not observed in solution. It contains two pentacoordinated [MnIII(tidf)]+ units, each one connected to a central hexacoordinated MnII ion through one µ-phenolate and one µ-acetate bridge.
dimanganese macrocyclic complexes; tetraiminodiphenolate; magnetic properties; spectroeletrochemistry; crystal structure
