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

Publikation: Beitrag in einer FachzeitschriftArtikel

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)]
Originalspracheenglisch
Seiten (von - bis)87139-87150
Seitenumfang12
FachzeitschriftRSC Advances
Jahrgang5
Ausgabenummer106
DOIs
PublikationsstatusVeröffentlicht - 2015

Schlagwörter

  • dinuclear copper pyridylmethylaminomethylphenolato complex prepn
  • crystal structure magnetic property dinuclear copper pyridylmethylaminomethylphenolato complex
  • spin density dinuclear copper pyridylmethylaminomethylphenolato complex

Fields of Expertise

  • Advanced Materials Science

Treatment code (Nähere Zuordnung)

  • Basic - Fundamental (Grundlagenforschung)

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