Ferromagnetic coupling and spin canting behaviour in heterobimetallic Re(IV)M(II/III) (M = Co(II/III), Ni(II)) species.

Three novel heterobimetallic Re(IV) compounds of formulae [ReBr(4)(μ-ox)M(4,7-Cl(2)phen)(2)]·CH(3)CN·CH(3)NO(2) [M = Co(II) (1) and Ni(II) (2)] and [ReBr(4)(ox)](3)[Co(III)(5,6-dmphen)(3)](2)·CH(3)CN·2CH(3)NO(2)·4H(2)O (3) [ox = oxalate, 4,7-Cl(2)phen = 4,7-dichloro-1,10-phenanthroline and 5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline] have been synthesised and the structures of 1 and 3 determined by single crystal X-ray diffraction. Compound 1 is an oxalato-bridged Re(IV)Co(II) heterodinuclear complex where the [ReBr(4)(ox)](2-) unit acts as a bidentate ligand towards the [Co(4,7-Cl(2)phen)(2)](2+) entity, the separation between Re(IV) and Co(II) across the oxalate being 5.482(1) Å. Compound 3 is an ionic salt whose structure is made up of [Re(IV)Br(4)(ox)](2-) anions and [Co(III)(5,6-dmphen)(3)](3+) cations plus acetonitrile, nitromethane and water as solvent molecules. The magnetic properties of 1-3 were investigated in the temperature range 1.9-300 K. Relatively large ferromagnetic interactions between Re(IV) and M(II) through the bis(bidentate) oxalato occur in 1 and 2 [J(ReM) = +11.0 (1) and +12.2 cm(-1) (2), the Hamiltonian being defined as Ĥ = -J(ReM)Ŝ(Re)·Ŝ(M)] which are explained on the basis of orbital symmetry considerations. A behaviour typical of a magnetically diluted Re(IV) complex with a large and positive value of zero-field splitting for the ground level (D(Re) = +43 cm(-1)) is observed for 3 in the high temperature range, whereas it exhibits spin canting in the low temperature domain as well as magnetic ordering below ca. 4.8 K.