Novel heterometallic polymeric lanthanide acetylacetonates with bridging cymantrenecarboxylate groups – synthesis, magnetism and thermolysis

Add time:09/29/2019    Source:sciencedirect.com

New isostructural complexes [Ln(CymCOO)(acac)2(H2O)]n (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), acac – acetylacetonate (pentane-2,4-dionate) anion) having a polymeric structure based on CymCOO-bridged {Ln(acac)2(H2O)} fragments were prepared by exchange reactions of hydrated Ln acetylacetonates with CymCOOH (Cym = (η5-C5H4)Mn(CO)3) in a CHCl3–EtOH–H2O mixture. For the synthesized complexes comprising diamagnetic cymantrenyl moieties the temperature dependences of the dc magnetic susceptibility were studied in the temperature range of 300–2 K under an applied magnetic field of 5 kOe. Slow magnetic relaxation was found in complexes 4 and 6. The thermal decomposition of the complexes was studied by TGA and DSC in the 30–600 °C temperature range in air and under Ar atmosphere. In the former case, the reaction affords LnMnO3 phases. The first step of the thermal decomposition of 6 was studied by the kinetic analysis. For the Dy and Ho complexes, standard thermodynamic functions were calculated from adiabatic calorimetry data. Manganites LnMnO3 (Ln = Eu, Gd, Tb, Dy) were synthesized from the corresponding complexes, and their magnetic properties were studied.

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