From the reaction of Li(cyclam-acetate), MnCl2. 4H(2)O, and KPF6 in methanol brown microcrystals of [Mn-III-Cl(cyclam-acetato)]PF6 (1) were obtained in the presence of air (cyclam-acetic acid = 1,4,8,11-tetraazacyclotetradecane-1-acetic acid). The reaction of I in aqueous NH3 solution with NaOCl produced 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 magnetochemistry as well as their electrochemistry have been investigated. The complexes [MnN(cyclam-acetato)](+/2+) were studied by theoretical calculations 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 spectroscopic parameters were successfully calculated and compared to experiment. A pictorial description of the bonding has been developed.