Cu-Pd-Cu and Cu-Pt-Cu linear frameworks: synthesis, magnetic properties, and theoretical analysis of two mixed-metal complexes of dipyridylamide (dpa), isostructural, and isoelectronic with [Cu3(dpa)4Cl2]+

Inorg Chem. 2007 Nov 12;46(23):9602-8. doi: 10.1021/ic070319l. Epub 2007 Oct 11.

Abstract

The synthesis and crystal structure of two heteronuclear compounds stabilized by four dipyridylamide (dpa) ligands is reported. Cu2Pd(dpa)4Cl2 (1) and Cu2Pt(dpa)4Cl2 (2) exhibit an approximate D4 symmetry and a linear metal framework. They are structurally similar to the homotrinuclear complexes M3(dpa)4L2 already characterized with various transition metals (M=Cr, Co, Ni, Cu, Rh, Ru). With 26 metal valence electrons, they are also isoelectronic to the oxidized form of the tricopper complex [Cu3(dpa)4Cl2]+ (3), previously characterized and investigated by Berry et al.10 The magnetic properties and the EPR spectra of 1 and 2 are reported. The results for 1 are interpreted in terms of a weak antiferromagnetic interaction (2J=-7.45 cm(-1) within the framework of the Heisenberg Hamiltonian H=-2JAB ŝAŝB) between the Cu(II) magnetic centers. For 2, the antiferromagnetic interaction sharply decreases to <1 cm(-1). These properties are at variance with those of (3), for which a relatively strong antiferromagnetic interaction (2J=-34 cm(-1)) had been reported. DFT/UB3LYP calculations reproduce the decrease of the magnetic interaction from 3 to 1 and assign it to the role of the nonmagnetic metal in the transference of the superexchange coupling. However, the vanishing of the magnetic interaction in 2 could not be reproduced at this level of theory and is tentatively assigned to spin-orbit coupling.