Molecular and electronic structure of [(MnN)-N-V(cyclam-acetato)]PF6. A combined experimental and DFT study

From the reaction of Li(cyclam-acetate), MnCl2. 4H(2)O, and KPF6 in methano l brown microcrystals of [Mn-III-Cl(cyclam-acetato)]PF6 (1) were obtained i n the presence of air (cyclam-acetic acid = 1,4,8,11-tetraazacyclotetradeca ne-1-acetic acid). The reaction of I in aqueous NH3 solution with NaOCl pro duced blue crystals of [(MnN)-N-V(cyclam-acetato)]PF6 (2), Complexes I and 2 were characterized by single-crystal X-ray crystallography, IR and Raman, electronic absorption, and H-1, C-13, and N-15 NMR spectroscopies. Their m agnetochemistry as well as their electrochemistry have been investigated. T he complexes [MnN(cyclam-acetato)](+/2+) were studied by theoretical calcul ations at the DFT and semiempirical levels in order to obtain more insight into the ground and excited states of the Mn-V=N unit. Structural and spect roscopic parameters were successfully calculated and compared to experiment . A pictorial description of the bonding has been developed.