Magnetism in Polyoxometalates: Anisotropic Exchange Interactions in the Co Moiety of [Co3W(D2O)2(ZnW9O34)2]12−—A Magnetic and Inelastic Neutron Scattering Study

作者：J.M. Clemente-Juan, Eugenio Coronado, Alejandro Gaita‐Ariño, Carlos Giménez‐Saiz, G. Chaboussant, H. U. Güdel, R. Burriel, H. Mutka · 发表于：Chemistry - A European Journal · 年份：2002 · DOI：10.1002/1521-3765(20021216)8:24<5701::aid-chem5701>3.0.co;2-t · 被引用次数：40 · 研究领域：Polyoxometalates: Synthesis and Applications、Magnetism in coordination complexes、Metal-Organic Frameworks: Synthesis and Applications

The ground-state properties of a Co3II moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2].40D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin-orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as H = -2 sigma a = x,y,z (Ja12 S1a S2a + Ja23 S2a S3a), where Ja are the components of the exchange interactions between the CoII ions. To reproduce the INS data, different orientations of the two anisotropic J tensors must be considered, and the following conditions had to be introduced: Jx12 = Jy23, Jy12 = Jx23, Jz12 = Jz23. This result was correlated with the molecular symmetry of the complex. The following set of parameters was obtained: Jx12 = Jy23 = 1.37, Jy12 = Jx23 = 0.218, and Jz12 = Jz23 = 1.24 meV. This set also reproduces in a satisfactory manner the specific heat, susceptibility, and magnetization properties of Co3.