Strong antiferromagnetic coupling in doubly N,O oximato-bridged dinuclear copper(II) complexes

The use of di-2-pyridyl ketone oxime, (py)pkoH, and phenyl 2-pyridyl ketone oxime, ppkoH, in copper(II) hexafluoroacetylacetonate chemistry is reported. The reaction of CuCl2·2H2O with one and two equivalents of ppkoH and Na(hfac), respectively, in CH2Cl2 affords the dinuclear complex [Cu2(hfac)2(ppko)2] (1) in excellent yield. The replacement of ppkoH by (py)pkoH gives the isostructural compound [Cu2(hfac)2{(py)pko}2] (2) in good yield. The CuII atoms in both 1 and 2 are doubly bridged by the oximate groups of two η1:η1:η1:μ2 ppko− and (py)pko− ligands, respectively. The bridging Cu–(R–NO)–Cu′ units are not planar, with the torsion angles being 23.2° (1) and 20.3° (2). A bidentate chelating hfac− ligand completes five-coordination at each square pyramidal metal ion. The hfac−-free reaction system CuCl2·2H2O/(py)pkoH/NEt3 (1:2:1) gives instead the mononuclear complex [CuCl{(py)pko}{(py)pkoH}] (3) in very good yield. The CuII atom is coordinated by two N,N′-bidentate (py)pko−/(py)pkoH chelates and a monodentate chloride anion resulting in a distorted square pyramidal geometry around the metal center. Variable-temperature, solid-state dc magnetic studies were carried out on the representative dinuclear complex 1 in the 2.0–300 K range. The data indicate a very strong antiferromagnetic exchange interaction and a resulting S = 0 ground state, which is well isolated from the S = 1 excited state. The J value of −720 cm−1 was derived from the fitting of the experimental data using the Hamiltonian H = −J(S1 · S2).

The copper(II) hexafluoroacetylacetonate/2-pyridyl oximes general reaction system has provided access to doubly, N,O oximato-bridged dinuclear complexes with a very strong antiferromagnetic coupling and a massive J value of −720 cm−1 for one representative complex.Figure optionsDownload as PowerPoint slide