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

Dalton Transactions : an International Journal of Inorganic Chemistry
Moumita PaitDebashis Ray

Abstract

Novel nitrito supported and μ4-oxido bridged Cu(II) aggregates have been found in two tetranuclear complexes, [Cu4(μ4-O)L2(μ(1,3)-ONO)4] (1) and [Cu4(μ4-O)L2(μ(1,3)-OAc)2(μ1,2-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 κ(2)O/O and κ(2)N/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 S(T) = 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,...Continue Reading

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