A series of manganese(II) complexes of bidentate NO donor set Schiff base ligands, together with corresponding mixed complexes containing 1,10-phenanthroline (phen), have been prepared by the electrochemical oxidation of a manganese anode in acetonitrile solutions of the Schiff bases (HL) and phen. The complexes formed are found to be of the form [Mn(L) 2 ] nH 2 O and [Mn(L) 2 (phen)] nH 2 O (n = 0-3). The single-crystal X-ray structure of [Mn(L 6 ) 2 (phen)] (L 6 = {N-[2-(4-methyl)phenyl]-salicylideneiminato}) reveals it to be a distorted octahedral manganese(II) complex, with the distortion occurring in the equatorial plane. Cyclic voltammetry and room-temperature magnetic studies indicate that the monomeric structure of [Mn(L 6 ) 2 (phen)] is representative of the whole series of mixed ligand compounds, whilst the magnetic behaviour of the complexes, formulated as [Mn(L) 2 ] nH 2 O, suggests that they may exist as polymeric species with strong antiferromagnetic coupling between the manganese centres.