A family of four new phenoxo-bridged binuclear manganese(III) complexes of the general formula, [Mn(L)(X)] 2 where L=[N,N′-bis(salicylidene)]propane-1,2-diamine and X=salicylaldehyde anion (sal − ) (1); NCS − (2); NCO − (3) and [Mn(L′)(N 3 )] 2 ·2C 2 H 5 OH (4) where L′=[N,N′-bis(2-hydroxyacetophenylidene)]propane-1,2-diamine has been prepared. The syntheses have been achieved by reacting manganese perchlorate with 1,2-diaminopropane and salicylaldehyde (or 2-hydroxyacetophenone for 4) or along with the respective pseudohalides so that the tetradentate Schiff base H 2 L or H 2 L′ is obtained in situ to bind the Mn(III) ion. The complexes have been characterized by IR spectroscopy, elemental analysis, crystal structure analysis and variable-temperature magnetic susceptibility measurements. The single crystal X-ray diffraction studies show that the compounds are isostructural containing dimeric Mn(III) units with bridging phenolate oxygen atoms. Low temperature magnetic studies indicate that the complexes 1–3 exhibit intradimer ferromagnetic exchange as well as single-molecule magnet (SMM) behavior while complex 4 is found to undergo an intradimer antiferromagnetic coupling.