Solvatomorphs of dimeric transition metal complexes based on the V4O12 cyclic anion as building block: Crystalline packing and magnetic properties |
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Authors: | V Paredes-García S Gaune M Saldías MT Garland R Baggio A Vega M Salah El Fallah A Escuer E Le Fur D Venegas-Yazigi E Spodine |
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Institution: | 1. Departamento de Química, Universidad Tecnológica Metropolitana, Chile;2. Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Chile;3. CIMAT, Universidad de Chile, Chile;4. Departamento de Física, Comisión Nacional de Energía Atómica, Argentina;5. Facultad de Ecología y Recursos Naturales, Universidad Nacional Andrés Bello, Chile;6. Departamento de Química Inorgánica, Universitat de Barcelona, Barcelona, Spain;7. Sciences Chimiques, UMR CNRS 6226, Rennes, France;8. Facultad de Química y Biología, Universidad de Santiago de Chile, Chile;9. Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Chile |
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Abstract: | Dinuclear {M(phen)2}2V4O12] · C6H12O · H2O (M = CoII 1, MnII 2, NiII 3 and CuII 4) and {Cu(phen)2}2V4O12] · 3.5H2O 5 has been prepared by biphasic and hydrothermal syntheses, respectively. All five structures exhibit the {V4O12}4? cluster in a chair-like configuration, covalently bonded to two M(phen)2]2+ fragments, producing a super-exchange magnetic phenomenon. The magnetic study of complexes 1–5 shows that they are very weak antiferromagnetically coupled systems, with J values of ?0.14, 2; ?0.64, 3 and ?0.23, 4 cm?1. Complexes 1 to 3 correspond to isostructural compounds in which the cyclovanadate group acts as a bidentate bridged ligand. In the copper complexes (4 and 5) the {V4O12}4? anion presents the novel monodentate bridging mode, and therefore a more significant distortion from the chair-like configuration. The mentioned complexes, together with that reported in the literature, permit to conclude that it is quite common for a single molecular species to exist in more than one crystalline arrangement. A detailed analysis of the structures of 1–4 shows that the crystal symmetry cannot be strictly centrosymmetric, due to the presence of the cyclohexanol molecule with a single –OH group in the lattice. |
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