Versatile binding properties of di-pyridyl ligands with Cu(II) complexes: The syntheses, structural characterization and thermal analysis of six new species

Salah S. Massoud, Elodie Druel, Marisa Dufort, Roger Lalancette, Jarrett Kitchen, Janusz Grebowicz, Ramon Vicente, Uday Mukhopadhyay, Ivan Bernal, Franz A. Mautner

Research output: Contribution to journalArticlepeer-review

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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)22-4,4′-bipy)(ClO4)4)]·H2O (3), [Cu2(cyclen)22-bpe)](ClO4)4 (4) and [Cu2(TPA)22-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).

Original languageEnglish (US)
Pages (from-to)3849-3857
Number of pages9
JournalPolyhedron
Volume28
Issue number17
DOIs
StatePublished - Nov 16 2009

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Keywords

  • Coordination polymer
  • Copper
  • Crystal structure
  • Di-pyridyl bridged
  • Magnetic behavior
  • Thermal analysis

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