Synthesis, structure and magnetic characterization of dinuclear copper(II) complexes bridged by bicompartmental phenolate

Salah S. Massoud, Thomas Junk, Febee R. Louka, Radovan Herchel, Zdenek Travnicek, Roland C. Fischer, Franz A. Mautner

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The reaction of Cu(II) salts with the bicompartmental 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (LCl-OH) ligand afforded four new dinuclear bridged phenoxido Cu(II) complexes. Three doubly bridged complexes namely [Cu2(μ-LCl-O)(μ-X)](ClO4)2 (1: X = OH-, 3: X = O2P(OPh)2-) and 2: [Cu2(μ-LCl-O)(μ-pz)(ClO4)]ClO4 (2) where pz = pyrazolyl anion, and one singly bridged-phenoxido, [Cu2(μ-LCl-O)(dca)2]PF6·2CH3CN (4·2CH3CN) (dca = dicyanamide anion). A complex similar to 4 was also obtained with 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (LMe-OH), [Cu2(μ-LMe-O)(dca)2]PF6·2CH3CN (5·2CH3CN) where in both cases dca are acting as terminal monodentate ligands. The complexes were structurally characterized by various spectroscopic techniques (IR, UV-visible and ESI-MS) and by single crystal crystallog. Magnetic susceptibility measurements at variable temp. revealed strong to very strong antiferromagnetic coupling (AF) in the doubly bridged complexes 1-3 and very weak AF interaction in the dicyanamido compds. 4 and 5. The DFT calcns. for the coupling consts., J were in agreement with the exptl. obsd. behavior. The trend in magnetic properties was attributed to the strength of overlap between the orbitals (dx2-y2/dx2-y2vs. dz2/dx2-y2vs. dz2/dz2) resulting from trigonal bipyramidal (TBP) or square pyramidal (SP) geometries. [on SciFinder(R)]
Original languageEnglish
Pages (from-to)87139-87150
Number of pages12
JournalRSC Advances
Issue number106
Publication statusPublished - 2015

Fields of Expertise

  • Advanced Materials Science

Treatment code (Nähere Zuordnung)

  • Basic - Fundamental (Grundlagenforschung)

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