Synthesis and Characterization of Four New Uranium(IV) Chlorophosphates: UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3) - Université de Lorraine Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2014

Synthesis and Characterization of Four New Uranium(IV) Chlorophosphates: UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3)

Résumé

The new uranium(IV) chlorophosphate compounds UCl4(POCl3) and [U2Cl9][PCl4] have been synthesized by the solid-state reactions of U, P2O5, and PCl5 at 648 K; the compounds UCl3(PO2Cl2) and U2Cl8(POCl3) have been synthesized at 648 K with the same reactants plus added S. Their structures are, respectively, chainlike, a simple salt, three-dimensional, and sheetlike. From ab initio calculations, U2Cl8(POCl3) and UCl3(PO2Cl2) are found to be ferromagnetic, whereas UCl4(POCl3) is found to be antiferromagnetic. U2Cl8(POCl3) is a strong metal, whereas UCl3(PO2Cl2) is a weaker metal. In contrast, UCl4(POCl3) has a finite band gap, with a value of 0.35 eV.

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Cristallographie
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Dates et versions

hal-01521314 , version 1 (11-05-2017)

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Matthew D. Ward, Ian Y. Chan, Sébastien Lebègue, James A. Ibers. Synthesis and Characterization of Four New Uranium(IV) Chlorophosphates: UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl2), and U2Cl8(POCl3). Inorganic Chemistry, 2014, 53 (18), pp.9969-9975. ⟨10.1021/ic501781h⟩. ⟨hal-01521314⟩
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