Mono-, di-, and oligonuclear complexes of Cu(II) ions and p-hydroquinone ligands: syntheses, electrochemical properties, and magnetic behavior

Four highly soluble square-planar Cu(II) and Ni(II) complexes of siloxy-salens (2SiCu, 2SiNi) and hydroxy-salens (2Cu, 2Ni) have been synthesized. An X-ray crystal structure analysis was performed on 2SiCu, 2SiNi, and 2Ni. The compounds have been investigated by cyclic voltammetry, UV-vis-NIR spectr...

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Published inInorganic chemistry Vol. 45; no. 3; p. 1277
Main Authors Margraf, Günter, Kretz, Tonia, Fabrizi de Biani, Fabrizia, Laschi, Franco, Losi, Serena, Zanello, Piero, Bats, Jan W, Wolf, Bernd, Remović-Langer, Katarina, Lang, Michael, Prokofiev, Andrei, Assmus, Wolf, Lerner, Hans-Wolfram, Wagner, Matthias
Format Journal Article
LanguageEnglish
Published United States 06.02.2006
Subjects
Copper - chemistry
Crystallography, X-Ray
Electrochemistry
Hydroquinones - chemistry
Ligands
Magnetics
Models, Molecular
Molecular Conformation
Nickel - chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Sensitivity and Specificity
Spectrophotometry, Infrared
Spectrophotometry, Ultraviolet
Stereoisomerism
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Summary:Four highly soluble square-planar Cu(II) and Ni(II) complexes of siloxy-salens (2SiCu, 2SiNi) and hydroxy-salens (2Cu, 2Ni) have been synthesized. An X-ray crystal structure analysis was performed on 2SiCu, 2SiNi, and 2Ni. The compounds have been investigated by cyclic voltammetry, UV-vis-NIR spectroelectrochemistry, and EPR spectroscopy. According to these results, the monooxidized species [2SiCu]+ and [2SiNi]+ are to be classified as Robin-Day class II and III systems, respectively. Magnetic measurements on the dinuclear (PMDTA)Cu(II) complex 1Cu2 x (PF6)2 with deprotonated 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)-benzene (1) linker revealed antiferromagnetic coupling between the two Cu(II) ions thereby resulting in an isolated dimer compound. Coordination polymers [1Cu]n(H2O)(2n) of Cu(II) ions and bridging p-hydroquinone linkers were obtained from CuSO4 x 5 H2O and 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)benzene. X-ray crystallography revealed linear chains running along the crystallographic a-direction and stacked along the b-axis. Within these chains, the Cu(II) ions are coordinated by two pyrazolyl nitrogen atoms and two p-hydroquinone oxygen atoms in a square-planar fashion.
ISSN:0020-1669
DOI:10.1021/ic051016z