Tetranuclear LnIII2MnII2 cymantrenecarboxylates. Synthesis, structure, thermolysis and magnetic properties

• 3d–4f-heterometallic “defective dicubane” cymantrenecarboxylates were synthesized.
• Thermolysis of obtained complexes under air affords LnMn2O5 and Mn2O3 phases.
• Dy complex exhibits the properties of single molecule magnet.

New organometallic 3d–4f-heterometallic carboxylates [LnIII2MnII2(μ3-OH)2(μ-O,η2-O2CCym)2(μ2-O2CCym)6(THF)4] (Ln = Dy, Ho; Cym = (η5-C5H4)Mn(CO)3) having “defective dicubane” structure were synthesized by means of partial destructive photolysis of the cymantrenecarboxylate anion in the presence of Ln3+, O2 and H2O. The magnetic susceptibilities (dc and ac) for the complexes were measured. Magnetic properties of Dy complex are indicative of its single molecule magnet behavior, complex of Ho displays slow relaxation of the magnetization at liquid helium temperature. Thermolysis of the complexes was studied by means of TG and DSC.

Novel 3d–4f heterometallic tetranuclear complexes, [LnIII2MnII2(μ3-OH)2(μ-O,η2-O2CCym)2(μ2-O2CCym)6(THF)4] (Ln = Dy, Ho; Cym = (η5-C5H4)Mn(CO)3) with “defective dicubane” structure were synthesized by means of partial destructive photolysis of CymCO2− anion in the presence of Ln3+, O2 and H2O, and characterized by X-ray analysis, thermal and magnetic studies. The complexes exhibit slow magnetic relaxation at temperature below 10 K.Figure optionsDownload as PowerPoint slide