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

Research output: Contribution to journalArticle

Abstract

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
Volume5
Issue number106
DOIs
Publication statusPublished - 2015

Fields of Expertise

  • Advanced Materials Science

Treatment code (Nähere Zuordnung)

  • Basic - Fundamental (Grundlagenforschung)

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