Mononuclear Transition Metal Cymantrenecarboxylates as Precursors for Spinel-Type Manganites

单核过渡金属氰基甲烯羧酸盐作为尖晶石型锰酸盐的前体

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Abstract

Novel mononuclear cymantrenecarboxylate complexes of transition metals, [Co(H(2)O)(6)](CymCO(2))(2)·4H(2)O (Cym = (η(5)-C(5)H(4))Mn(CO)(3)) (1), [Ni(H(2)O)(6)](CymCO(2))(2)·4H(2)O (2), [Zn(H(2)O)(6)](CymCO(2))(2)·4H(2)O (3), [Co(CymCO(2))(2)(imz)(2)] (imz = imidazole, 4), [Co(CymCO(2))(2)(bpy)(2)]·2PhMe (bpy = 2,2'-bipyridyl, 5), [Ni(CymCO(2))(bpy)(2)(H(2)O)][CymCO(2)]·0.5MePh·2H(2)O (6), [Cu(CymCO(2))(2)(imz)(2)] (7), and [Cu(CymCO(2))(2)(bpy)(H(2)O)] (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/k(B)) 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 MMn(2)O(4); for the cases of copper complexes, the mixtures of CuMn(2)O(4) and CuO were found in the products.

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