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Mononuclear Transition Metal Cymantrenecarboxylates as Precursors for Spinel-Type Manganites
Authors:Pavel S Koroteev  Andrey B Ilyukhin  Andrey V Gavrikov  Konstantin A Babeshkin  Nikolay N Efimov
Institution:N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 31, 119991 Moscow, Russia; (A.B.I.); (A.V.G.); (K.A.B.); (N.N.E.)
Abstract:Novel mononuclear cymantrenecarboxylate complexes of transition metals, Co(H2O)6](CymCO2)2·4H2O (Cym = (η5-C5H4)Mn(CO)3) (1), Ni(H2O)6](CymCO2)2·4H2O (2), Zn(H2O)6](CymCO2)2·4H2O (3), Co(CymCO2)2(imz)2] (imz = imidazole, 4), Co(CymCO2)2(bpy)2]·2PhMe (bpy = 2,2′-bipyridyl, 5), Ni(CymCO2)(bpy)2(H2O)]CymCO2]·0.5MePh·2H2O (6), Cu(CymCO2)2(imz)2] (7), and Cu(CymCO2)2(bpy)(H2O)] (8), were obtained and characterized by single-crystal X-ray analysis. Complexes 1–3 are isostructural. Magnetism of the Co complexes 1, 4, and 5 was studied; it was shown that they exhibit the properties of field-induced single-molecule magnets with magnetization reversal barriers (ΔE/kB) of 44, 13, and 10 K, respectively. Thermal decomposition of complexes 1–8 was studied by means of DSC and TGA methods. The final products of thermolysis of 1–6 in air, according to powder XRD data, are the pure spinel phases MMn2O4; for the cases of copper complexes, the mixtures of CuMn2O4 and CuO were found in the products.
Keywords:cymantrenecarboxylate  transition metals  heterometallic complexes  thermolysis  spinel  manganite  magnetic properties  single-ion magnet
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