Tetranuclear clusters containing a CrIII-doped MnIII4O2 core: syntheses, structures, and magnetic properties

The oxidation of MnII carboxylates by (NBu4)Cr2O7 in the presence of different phosphonic acids and chelating ligands results in six CrIII-doped tetranuclear manganese clusters formulated Mn3CrO2(O2CCH3)4(O3PC5H4N)2(bpy)2] (1), Mn3CrO2(O2CCH3)4(O3PC5H4N)2(phen)2] (2), Mn3CrO2(O2CPh)4(O3PC5H4NO)2(phen)2] (3), Mn3CrO2(O2CPh)4(O3PC6H11)2(bpy)2] (4), Mn 3CrO2(O2CPh)4(O3PC6H11)2(phen) 2] (5), and Mn3CrO2(O2CCH3)4(O3PC6H11)2(bpy)2] (6). Single-crystal X-ray analyses reveal that all the compounds contain similar M4O2]8+ cores with the four metal sites arranged in planar topologies. The metal ions within the core are bridged by both carboxylate and phosphonate ligands. Temperature-dependent magnetic measurements show that in all cases dominant antiferromagnetic interactions are propagated between the metal centers. The ac magnetic measurements on compounds 5 and 6 reveal that both the in-phase and the out-of-phase signals are frequency dependent, characteristic of single-molecule magnet behaviors.