Magnetic Properties of Diruthenium(II,III) Carboxylate Compounds with Large Zero-Field Splitting and Strong Antiferromagnetic Coupling

The magnetic properties of mixed-valent compounds of general formula Ru2Cl(μ-O2CR)4 [R = CH2−CH3 (1), C(Me)CHEt) (2)] have been studied in the 2−300 K temperature range. This magnetic study also includes a revision of the magnetic properties of the complex Ru2Cl(μ-O2CCMePh2)4 (3). Compounds 1−3 show a linear structure and a strong antiferromagnetic coupling between the diruthenium units through the chlorine atoms according to previous studies. Two fitting models to explain the magnetic properties of these complexes that incorporate a large zero-field splitting together with a strong antiferromagnetic coupling are described. These models consider that each diruthenium unit (S = 3/2) is magnetically coupled to the nearest diruthenium unit and ignores the longer distance magnetic coupling. The fitting models were found to be successful in fitting the magnetic data of the linear diruthenium(II,III) complexes. The zero-field splitting, D, and the antiferromagnetic coupling, zJ, vary from 37.8 to 48.0 cm-1 and from −7.43 to −13.30 cm-1, respectively, for complexes. The D values are similar to those calculated for the nonlinear diruthenium(II,III) compounds and confirm the validity of the proposed fitting models.