Electronic structure and magnetic coupling of two dinuclear trigonal bipyramidal cobalt(II) complexes

The EPR spectra of zinc-doped (bis(N-methylsalicylaldiminato)cobalt(II), (Zn, Co) SALMe, which was found to be dinuclear, and of zinc-doped bis(N,N-bis(2-(diethylamino)ethyl)-2-hydroxyethylamino-O)dicobalt(II)diperchlorate, (Zn, Co)n3o, were recorded at liquid helium temperature and X-band frequency. The polycrystalline powder spectra of (Zn, Co)SALMe were interpreted within an effective S = 1/2 spin hamiltonian formalism with g1 = 1.8, g2 = 2.7, g3 = 6.2, while those of (Zn, Co)n3o showed only one band at g= 6.9. The single crystal spectra for the latter yielded g1 = 0.31(4), g2 = 0.84(4), g3 = 6.86(2). The electronic structure of the complexes was calculated using the AOM, and the lowest Kramers doublet for CoSALMe was found to be ±1/2 while a ±3/2 doublet was found for Con3o. The temperature dependence of the magnetic susceptibility of CoSALMe was measured between 295 and 4.2 K. The data were fitted with two different methods which either took into account or neglected the zero-field splitting of single ions. The coupling was found to be antiferromagnetic with J = 9.8(2) cm-1 (J is defined through the hamiltonian View the MathML source = JS1·S2). The extent of the magnetic interaction between the metal ions for both the complexes was discussed on the basis of a structural analysis.