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• W2090728181 abstract "Unusual spin coupling between MoIII and MnII cyano-bridged ions in bimetallic molecular magnets based on the [MoIII(CN)7]4- heptacyanometalate is analyzed in terms of the superexchange theory. Due to the orbital degeneracy and strong spin−orbit coupling on MoIII, the ground state of the pentagonal-bipyramidal [MoIII(CN)7]4- complex corresponds to an anisotropic Kramers doublet. Using a specially adapted kinetic exchange model we have shown that the MoIII−CN−MnII superexchange interaction is extremely anisotropic: it is described by an Ising-like spin Hamiltonian J for the apical pairs and by the Jz + Jxy( + ) spin Hamiltonian for the equatorial pairs (in the latter case Jz and Jxy can have opposite signs). This anisotropy resulted from an interplay of several Ising-like ( ) and isotropic (SMoSMn) ferro- and antiferromagnetic contributions originating from metal-to-metal electron transfers through the π and σ orbitals of the cyano bridges. The MoIII−CN−MnII exchange anisotropy is distinct from the anisotropy of the g-tensor of [MoIII(CN)7]4-; moreover, there is no correlation between the exchange anisotropy and g-tensor anisotropy. We indicate that highly anisotropic spin−spin couplings (such as the Ising-like J ) combined with large exchange parameters represent a very important source of the global magnetic anisotropy of polyatomic molecular magnetic clusters. Since the total spin of such clusters is no longer a good quantum number, the spin spectrum pattern can differ considerably from the conventional scheme described by the zero-field splitting of the isotropic spin of the ground state. As a result, the spin reorientation barrier of the magnetic cluster may be considerably larger. This finding opens a new way in the strategy of designing single-molecule magnets (SMM) with unusually high blocking temperatures. The use of orbitally degenerate complexes with a strong spin−orbit coupling (such as [MoIII(CN)7]4- or its 5d analogues) as building blocks is therefore very promising for these purposes." @default.
• W2090728181 created "2016-06-24" @default.
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• W2090728181 date "2003-07-22" @default.
• W2090728181 modified "2023-10-11" @default.
• W2090728181 title "Mechanism of a Strongly Anisotropic Mo^III−CN−Mn^II Spin−Spin Coupling in Molecular Magnets Based on the [Mo(CN)₇]⁴^- Heptacyanometalate: A New Strategy for Single-Molecule Magnets with High Blocking Temperatures" @default.
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• W2090728181 doi "https://doi.org/10.1021/ja029518o" @default.
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