0000000000335994

AUTHOR

Herma Büttner

Anisotropic exchange coupling in the Keggin derivative K8[Co2(D2O)(W11O39)] · n D2O

Abstract 20 g of the fully deuterated title compound have been prepared in polycrystalline form and investigated by inelastic neutron scattering using both thermal and cold neutrons. Magnetic dimer excitations were observed and the energy-splitting pattern resulting from the exchange coupling within the Co 2+ dimer was determined. The coupling is highly anisotropic with the parameter values J =−2.24 meV and η =0.33 based on the effective coupling Hamiltonian H =−2J[S 1z S 2z +η(S 1x S 2x +S 1y S 2y )] . The anisotropy results mainly from the single-ion anisotropy of the Co 2+ ion in the distorted octahedral coordination.

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Magnetic Polyoxometalates:  Anisotropic Antiferro- and Ferromagnetic Exchange Interactions in the Pentameric Cobalt(II) Cluster [Co3W(D2O)2(CoW9O34)2]12-. A Magnetic and Inelastic Neutron Scattering Study

The ground-state properties of the pentameric Co(II) cluster [Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)](12-) were investigated by combining magnetic susceptibility and low-temperature magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na(12)[Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)].46D(2)O. The encapsulated magnetic Co(5) unit consists of three octahedral and two tetrahedral oxo-coordinated Co(II) ions. Thus, two different types of exchange interactions are present within this cluster: a ferromagnetic interaction between the octahedral Co(II) ions and an antiferromagnetic interaction between the octahedral and the tetrahedral…

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Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering:  Evidence for Ferromagnetic Exchange Interactions and Spin Anisotropy in the Tetrameric Nickel(II) Cluster [Ni4(H2O)2(PW9O34)2]10- and Comparison with the Magnetic Properties

The ground-state properties of the tetranuclear Ni2+ cluster [Ni4(H2O)2(PW9O34)2]10- were investigated by combining magnetic susceptibility and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K6Na4[Ni4(H2O)2(PW9O34)2]·24H2O. The temperature dependence of the magnetic susceptibility indicates a ferromagnetic coupling of the four constituent Ni2+ ions (s = 1), and a low-temperature magnetization study provides the magnitude of the S = 4 ground-multiplet splitting due to the single-ion anisotropy of the Ni2+ ions. Besides a more direct and precise determination of the anisotropic S = 4 ground-multiplet splitting, INS enabled t…

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Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering:  Evidence for Anisotropic Ferromagnetic Exchange Interactions in the Tetrameric Cobalt(II) Cluster [Co4(H2O)2(PW9O34)2]10-. Comparison with the Magnetic and Specific Heat Properties

The ground-state properties of the tetranuclear Co2+ cluster [Co4(H2O)2(PW9O34)2]10- were investigated by combining specific heat, magnetic susceptibility, and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K10[Co4(H2O)2(PW9O34)2]·22H2O. As a result of the single ion anisotropy of the octahedral Co2+, the appropriate exchange Hamiltonian of the Co4 spin cluster is anisotropic. INS turns out to be essential for the determination of energy splittings in the ground state resulting from the coupling. Besides the energy pattern, INS provides information about the wave functions of the split ground-state components of the spin c…

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Magnetic excitations in polyoxometalate tetrameric clusters

Abstract The metal-oxide clusters with formula [M4(D2O)2(PW9O34)2]10− which contain a tetrameric magnetic cluster M4O16 provide an ideal series for the study of magnetic exchange interactions in polymetallic molecular clusters. To get a more direct information on the splitting of the spin states caused by the exchange interactions we have performed inelastic neutron scattering measurements on the Co, Mn and Ni clusters. Magnetic excitations have been observed in the range 0.5–6 meV. A tentative interpretation of these data from a Heisenberg exchange Hamiltonian and a single ion zero-field splitting is presented for Ni cluster.

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Magnetic Excitations in Tetrameric Clusters of Polyoxometalates Observed by Inelastic Neutron Scattering. Evidence for Anisotropic Exchange Interactions in Cobalt(II) Clusters.

Magnetic excitations in tetranuclear clusters of exchange-coupled metal ions encapsulated by polyoxotungstate ligands (1) have been observed by inelastic neutron scattering (INS) in the salts K10[M4(H2O)2(PW9O34)2]·nH2O, where M2+ = Mn, Co, and Ni. INS provides a much deeper and more detailed insight into the nature of the magnetic coupling in these clusters than bulk techniques. In particular, anisotropic exchange interactions are evidenced in the ferromagnetic Co4 cluster.

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