Heterotetranuclear Oxalato-Bridged (Re3MII)-M-IV (M = Mn, Fe, Co, Ni, Cu) Complexes: A New Example of a Single-Molecule Magnet (M = Ni)

International audienceThe use of the mononuclear species (NBu4)(2)[(ReCl4)-Cl-IV(OX)] (NBu4+ = tetra-n-butylammonium cation; ox = oxalate dianion) as a ligand toward fully solvated divalent first-row transition-metal ions affords the tetranuclear complexes (NBu4)(4)[{(ReCl4)-Cl-IV(u-ox)}(3)M-II] with M = Mn (1), Fe (2), Co (3), Ni (4), and Cu (5). Their structure is made up of discrete [{ReCl4(mu-ox)}(3)M](4-) anions and bulky NBu4+ cations. The complexes 2-5 crystallize in the triclinic system with space group Pi; 2 and 5 as well as 3 and 4 are isostructural. The Re and M atoms exhibit somewhat distorted ReCl4O2 and MO6 octahedral surroundings, with the oxalate groups adopting the bis-bidentate bridging mode. Magnetic susceptibility measurements on polycrystalline samples of 1-5 in the temperature range 1.9-300 K show the occurrence of intramolecular antiferromagnetic [J = -1.30 cm(-1) (1)] and ferromagnetic couplings [J = +1.62 (2), +3.0 (3), +16.3 (4), and +4.64 cm(-1) (5)], with the Hamiltonian being defined as H = -J[S-M(S-Re1 + S-Re2 + S-Re3)]. Compound 4 is the first example of an oxalato-bridged heterometallic species that behaves as a single-molecule magnet with a ground-state spin S = 11/2 and D = -0.8(1) cm(-1), as shown by the study of its static and dynamic magnetic properties and a high-frequency electron paramagnetic resonance study on polycrystalline samples together with detailed micro-SQUID measurements on single crystals