Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW12O40]4−: a synthetic, structural and computational investigation

Shadi Derakhshanrad, Masoud Mirzaei, Atefeh Najafi, Chris Ritchie, Antonio Bauzá, Antonio Frontera, Joel T. Mague

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As an extension of our continued interest in the preparation of inorganic–organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ-1,10-phenanthroline-2,9-dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(C14H6N2O4)3(H2O)9(SiW12O40)]·12H2O}n or Na[Dy(PDA)(H2O)3]3[SiW12O40]·12H2O (1), and sodium aqua tris[tetraaqua(μ-4-hydroxypyridine-2,6-dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(C7H3NO5)3(H2O)13(SiW12O40)]·12H2O}n or Na(H2O)[Pr(pydc-OH)(H2O)4]3[SiW12O40]·12H2O (2) (in which H2PDA is 1,10-phenanthroline-2,9-dicarboxylic acid and H2pydc-OH is 4-hydroxypyridine-2,6-dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X-ray diffraction methods. Structural characterization by single-crystal X-ray diffraction reveals that these compounds consist of [SiW12O40]4− Keggin-type polyoxometalates (POMs), where a single {W3O13} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion–π interactions, resulting in three-dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both 1 and 2, and have been rationalized using molecular electrostatic potential (MEP) surface calculations.

Original languageEnglish
Pages (from-to)1300-1309
Number of pages10
JournalActa Crystallographica Section C: Structural Chemistry
Issue number11
Publication statusPublished - 1 Nov 2018
Externally publishedYes


  • computational chemistry
  • crystal structure
  • DFT calculations
  • Keggin
  • lanthanoid
  • MEP
  • molecular electrostatic potential
  • phenanthroline
  • polyoxometalates
  • POM
  • preorganized ligand
  • X-ray

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