title: Heterotetranuclear oxalato-bridged Re(IV)3M(II) (M = Mn, Fe, Co, Ni, Cu) complexes: a new example of a single-molecule magnet (M = Ni).
abstract: The use of the mononuclear species (NBu(4))(2)[Re(IV)Cl(4)(ox)] (NBu(4)(+) = tetra-n-butylammonium cation; ox = oxalate dianion) as a ligand toward fully solvated divalent first-row transition-metal ions affords the tetranuclear complexes (NBu(4))(4)[{Re(IV)Cl(4)(mu-ox)}(3)M(II)] with M = Mn (1), Fe (2), Co (3), Ni (4), and Cu (5). Their structure is made up of discrete [{ReCl(4)(mu-ox)}(3)M](4-) anions and bulky NBu(4)(+) cations. The complexes 2-5 crystallize in the triclinic system with space group P1; 2 and 5 as well as 3 and 4 are isostructural. The Re and M atoms exhibit somewhat distorted ReCl(4)O(2) and MO(6) 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.
authors.affiliation: Departament de Química Inorgànica/Instituto de Ciencia Molecular, Facultat de Química, Universitat de València, Avenida Dr. Moliner 50, 46100 Burjassot, València, Spain.
authors.forename: José
authors.initials: J
authors.lastname: Martínez-Lillo
authors.forename: Donatella
authors.initials: D
authors.lastname: Armentano
authors.forename: Giovanni
authors.initials: G
authors.lastname: De Munno
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Wernsdorfer
authors.forename: Juan Modesto
authors.initials: JM
authors.lastname: Clemente-Juan
authors.forename: J
authors.initials: J
authors.lastname: Krzystek
authors.forename: Francesc
authors.initials: F
authors.lastname: Lloret
authors.forename: Miguel
authors.initials: M
authors.lastname: Julve
authors.forename: Juan
authors.initials: J
authors.lastname: Faus