Synthesis, structure, and properties of LnBiI6•13H2O (Ln = La, Nd)

Аннотация

Two new iodobismuthates with the composition LnBiI₆•13H₂O (Ln = La, Nd) were synthesized and their crystal structures were determined. The compound LaBiI₆•13H₂O crystalizes in the orthorhombic space group Pna2₁, a = 24.206(5), b = 8.405(1), c = 26.360(5) Å; the compound NdBiI₆•13H₂O crystalizes in the monoclinic space group P2₁/n, a = 14.553(3), b = 13.386(3), c = 27.541(6) Å, β = 92.80(3)°. In both crystal structures, the cations Ln(H₂O)₉³⁺ and the anions BiI₆^3– alternate, forming a NaCl-type structure, and the structures themselves differ in the arrangement of water of crystallization that leads to the formation of dissimilar systems of hydrogen bonds. Both compounds undergo decomposition when heated, which is accompanied first by a partial liberation of water molecule, followed by pyrohydrolysis to form oxoiodides LnOI as final solid products. According to optical measurements, the band gap of the obtained compounds was equal to 1.78 (La) and 1.71 (Nd) eV.