Versatile binding properties of di-pyridyl ligands with Cu(II) complexes: The syntheses,structural characterization and thermal analysis of six new species |
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| Authors: | Salah S Massoud Elodie Druel Marisa Dufort Roger Lalancette Jarrett Kitchen Janusz Grebowicz Ramon Vicente Uday Mukhopadhyay Ivan Bernal Franz A Mautner |
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| Institution: | 1. Department of Chemistry, University of Louisiana at Lafayette, P.O. Box 44370, Lafayette, LA 70504-4370, USA;2. Department of Chemistry, Rutgers University, Olson Laboratories, Newark, NJ 07102, USA;3. Department of Natural Sciences, University of Houston-Downtown, Houston, TX 77002, USA;4. Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain;5. Department of Chemistry, University of Houston, Houston, TX 77204, USA;6. Institut für Physikalische and Theoretische Chemie, Technische Universität Graz, A-8010 Graz, Austria |
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| Abstract: | A novel series of 4,4′-bipyridine- and 1,2-bis(4-pyridyl)ethane-Cu(II) complexes were synthesized using a variety of amine ligands (DPA = di(2-pyridylmethyl)amine, Medpt = 3,3′-diamino-N-methyldipropylamine, Hbpca = bis(2-pyridylcarbonyl)amine, TPA = tris(2-pyridylmethyl)amine) and cyclen = 1,4,7,10-tetraazacyclododecane). Different complexes were obtained including mononuclear Cu(cyclen)(4,4′-bipy)](ClO4)2 (1), dinuclear {Cu(μ2-bpca)(4,4′-bipy)(H2O)]ClO4}2 (2), Cu2(DPA)2(μ2-4,4′-bipy)(ClO4)4)]·H2O (3), Cu2(cyclen)2(μ2-bpe)](ClO4)4 (4) and Cu2(TPA)2(μ2-bpe)](ClO4)4 (5) and the 1-D polymer, {Cu(Medpt)(μ2-4,4′-bipy)](ClO4)2}n (6). In the 1–6 samples, cooling up to 100 K produces only the expected, minor, changes in cell constants given no space group changes. Therefore, data for the 100 K structures are reported only. Single-crystal X-ray crystallography reveals the monodentate coordination of the 4,4′-bipy in 1 and 2, and the bridged nature of the di-pyridyl ligands in the dinuclear complexes 2–5 and in the polymeric complex 6. In this series, structures 3–6 consist of the 4,4′-bipy or bpe bridging the two Cu(II) centers, the coordination by the tri- or the tetra-N donors of the amine, and the ClO4? groups as counter ions in 4–6 complexes. In the complexes 3–6, the Cu···Cu distances across the bridged di-pyridyl ligands were found to be greater than 11 Å. The magnetic properties of complex 3 reveal no evidence for magnetic coupling between the two Cu(II) centers (J = ?0.58 cm?1). |
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