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Issue 13, 2015
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Two types of nitrito support for μ4-oxido-bridged [Cu4] complexes: synthesis, crystal structures, magnetic properties and DFT analysis

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Abstract

Novel nitrito supported and μ4-oxido bridged CuII aggregates have been found in two tetranuclear complexes, [Cu44-O)L21,3-ONO)4] (1) and [Cu44-O)L21,3-OAc)21,2-NO2)2] (2), of the chiral Schiff base HL (HL = 4-methyl-2,6-bis-(1-phenyl-ethylimino)-methylphenol). The structures contain either in situ generated or externally added peripheral μ-nitrito groups, in κ2O/O and κ2N/O bridging modes. Four NO2 bridges in 1 and two AcO co-ligands along with two NO2 bridges in 2 are essential for the stabilization of these tetranuclear aggregates. The complexes have been characterized by X-ray crystal structure determination, spectroscopic and magnetic measurements, and density functional theory (DFT) analysis. They are formed from the assembly of two [Cu2L]3+ fragments around a water-derived oxido ligand under the control of nitrite or mixed nitrite/acetate bridges. Variable temperature magnetic susceptibility measurements reveal strong intramolecular antiferromagnetic exchange interactions within the tetranuclear clusters to yield ST = 0 ground state. The capacity of the two different nitrite bridging modes to mediate magnetic coupling has been examined through measurements and numerical fitting procedures, and rationalized by means of DFT calculations.

Graphical abstract: Two types of nitrito support for μ4-oxido-bridged [Cu4] complexes: synthesis, crystal structures, magnetic properties and DFT analysis

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Publication details

The article was received on 20 Oct 2014, accepted on 09 Feb 2015 and first published on 11 Feb 2015


Article type: Paper
DOI: 10.1039/C4DT03224A
Citation: Dalton Trans., 2015,44, 6107-6117
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    Two types of nitrito support for μ4-oxido-bridged [Cu4] complexes: synthesis, crystal structures, magnetic properties and DFT analysis

    M. Pait, M. Shatruk, J. Lengyel, S. Gómez-Coca, A. Bauzá, A. Frontera, V. Bertolasi and D. Ray, Dalton Trans., 2015, 44, 6107
    DOI: 10.1039/C4DT03224A

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