Four new dysprosium and neodymium octamolybdate hydrates: assembly of RE2(Mo8O27) sheets and topotactic transformations.
Four new Dy and Nd hydrated octamolybdate materials have been prepared: [Dy(2)(H(2)O)(12)](Mo(8)O(27)) x 8 H(2)O, [Dy(2)(H(2)O)(6)](Mo(8)O(27)), [Nd(2)(H(2)O)(12)](Mo(8)O(27)) x 6 H(2)O, and [Nd(2)(H(2)O)(6)]Mo(8)O(27) x 3 H(2)O. They adopt one known and three new structure types, which we have determined ab initio from powder X-ray diffraction data. The four compounds contain the same basic structural building block, in the form of RE(2)Mo(8)O(27) (RE = Dy, Nd) chains, which are arranged differently for the two rare earths in the fully hydrated precursor materials. [Dy(2)(H(2)O)(12)](Mo(8)O(27)) x 8 H(2)O comprises isolated Dy(2)Mo(8)O(27) chains assembled in a zigzag manner along the a axis with interspersed crystallized water molecules, which differs from the parallel arrangements of isolated Nd(2)Mo(8)O(27) chains in [Nd(2)(H(2)O)(12)](Mo(8)O(27)) x 6 H(2)O. Partial dehydration of the two precursors leads to new phases [Dy(2)(H(2)O)(6)](Mo(8)O(27)) and [Nd(2)(H(2)O)(6)]Mo(8)O(27) x 3 H(2)O, respectively, prior to complete dehydration, which leads to initially amorphous and eventually crystalline rare-earth molybdenum mixed metal oxides. Both initial transformations occur topotactically. Partial dehydration of the Dy phase condenses the assembly of the Dy(2)Mo(8)O(27) chains principally along the a axis, leading to a 3-dimensional (3D) framework, with each Dy bridging two (Mo(8)O(27))(6-) sheets in the product. The partial dehydration of the Nd precursor condenses the assembly of Nd(2)Mo(8)O(27) chains along the [110] axis, leading to a 3D framework where each Nd bridges three (Mo(8)O(27))(6-) units. Both new dysprosium octamolybdates adopt noncentrosymmetric polar structures in space group P2(1) and are second harmonic generation (SHG) active.
Department of Chemistry, University of Durham, Science Site, South Road, Durham DH1 3LE, England, United Kingdom.
Xiaojun
X
Kuang
Ivana R
IR
Evans