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Title: Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00133a049· OSTI ID:5455832

New ternary metal borides, EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/, have been synthesized from the elements. The compounds were found to crystallize with the structure type of NdCo/sub 4/B/sub 4/. Effective paramagnetic moments derived from chi/sup -1/vs. T plots over the range 1.8-800 K are in good agreement with theoretical values according to a Hund's rule ground-state /sup 8/S/sub 1/2/ for a free Eu/sup 2 +/ ion. Complete solid solution was found for mixed crystals of CeOs/sub 4/B/sub 4/-CeIr/sub 4/B/sub 4/ (arc melted, quenched, NdCo/sub 4/B/sub 4/-type structure) revealing a positive deviation from Vegard's law. Magnetic susceptibilities were determined for the temperature range 1.8-1000 K. At high temperature the magnetic properties are characterized by Van Vleck paramagnetism of closely spaced multiplets due to admixture of the excited term J = /sup 7///sub 2/ of the Ce/sup 3 +/F/sub 5///sub 2/ ground state. At lower temperatures the paramagnetic behavior of cerium changes from that of a practically pure Ce/sup 4 +/ state in CeOs/sub 4/B/sub 4/ (..mu../sub eff/ = 0.49 ..mu beta..) to that of a pronounced Ce/sup 3 +/ state in CeIr/sub 4/B/sub 4/ (..mu../sub eff/ = 2.21 ..mu beta..) presumably due to the larger iridium metal framework and/or the higher electron-to-atom ratio. At very low temperatures, less than or equal to 3.5 K, ferromagnetic ordering was observed for CeIr/sub 4/B/sub 4/ and CeIr/sub 3/Os/sub 1/B/sub 4/. For comparison, the magnetic behavior was studied over the range 1.5-300 K of the pseudobinary sections PrOs/sub 4-x/Ir/sub x/B/sub 4/ and SmOs/sub 4-x/Ir/sub x/B/sub 4/. Although a slight negative deviation from Vegard's law was observed, there was practically no change from a valence state of Sm/sup 3 +/ for samarium. On the basis of Miedema's model, a thermodynamic calculation for the valence change (Ce/sup III/ ..-->.. Ce/sup IV/, Eu/sup II/ ..-->.. Eu/sup III/) has been found to be in good accord with the magnetic behavior observed. 7 figures, 4 tables.

OSTI ID:
5455832
Journal Information:
Inorg. Chem.; (United States), Vol. 21:3
Country of Publication:
United States
Language:
English

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