A series of trinuclear sandwich-like cyanide-bridged iron(III)-manganese(II) complexes: synthesis, crystal structures, and magnetic properties

Abstract

Four pyridinecarboxamide iron dicyanide building blocks and one Mn(III) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a series of trinuclear cyanide-bridged FeIII–MnII complexes: {[Mn(DMF)2 (MeOH)2][Fe(bpb)(CN)2]2}·2DMF (1), {[Mn(MeOH)4][Fe(bpmb)(CN)2]2}·2MeOH·2H2O (2), {[Mn(MeOH)4][Fe(bpdmb)(CN)2]2}·2MeOH·2H2O (3) and {[Mn(MeOH)4][Fe(bpClb)(CN)2]2}·4MeOH (4) (bpb2− = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2− = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpdmb2− = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, bpClb2− = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate). Single-crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. Investigation of the magnetic properties of these complexes reveals antiferromagnetic coupling between the neighboring Fe(III) and Mn(II) centers through the bridging cyanide group. A best fit to the magnetic susceptibilities of complexes 1 and 3 gave the magnetic coupling constants J = −1.59(2) and −1.32(4) cm−1, respectively.