title: The synthesis and characterization of four new uranium(IV) chlorophosphates: UCl₄(POCl₃), [U₂Cl₉][PCl₄], UCl₃(PO₂Cl₂), and U₂Cl₈(POCl₃).
abstract: 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.
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Ward
authors.forename: Ian Y
authors.initials: IY
authors.lastname: Chan
authors.forename: Sébastien
authors.initials: S
authors.lastname: Lebègue
authors.forename: James A
authors.initials: JA
authors.lastname: Ibers