New Path for Polyoxometalates: Controlled Synthesis and Characterization of Metal-Substituted Tungstosulfates

Hikaru Hirabaru, Daisuke Kawamoto, Miho Ohnishi, Hiromi Ota, Masahiro Sadakane, Kazumichi Yanagisawa, Takuya Hasegawa, Tadaharu Ueda

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Currently, a large number of metal-substituted tungstophosphates and tungstosilicates have been prepared with well-controlled systematic procedures, and many of them have been applied to various fields, such as catalysis and materials, because of their fascinating chemical properties. In addition, the diverse structures of metal-substituted polyoxometalates (POMs) are quite interesting as molecular architectures. However, there have been fewer reports on the synthesis of metal-substituted POMs with other hetero atoms. In the present study, controlled and systematic synthetic procedures for Wells–Dawson-type metal-substituted tungstosulfates, [S2MW17O61]6– (M = Mn, Co, Ni, Cu), were developed via a ring-shaped lacunary tungstosulfate, [(S2W14O54)3]32– prepared from the weak base treatment of K4[S2W18O62] in aqueous solution. [(S2W14O54)3]32– and [S2MW17O61]6– were structurally characterized by elemental analysis, X-ray crystallography and ESI-MS. [(S2W14O54)3]32– has a different type of structure with a cavity than Preyssler-type POMs, [X5W30O110]n–, and the other POMs, [X8W48O184]40– (X = P, As). In addition, IR, Raman and UV/Vis spectra as well as cyclic voltammograms of all of the POMs isolated in the present study were obtained and compared with the corresponding Wells–Dawson-type metal-substituted tungstophosphates. The synthetic procedures for [S2MW17O61]6– from [S2W18O62]4– via [(S2W14O54)3]32– could open a new path for tungstosulfate chemistry, such as widespread tungstophosphate and tungstosilicate chemistry.

Original languageEnglish
JournalEuropean Journal of Inorganic Chemistry
DOIs
Publication statusAccepted/In press - 2019 Jan 1
Externally publishedYes

Keywords

  • Metal substitution
  • Polyoxometalates
  • Synthesis design
  • Tungsten
  • Wells-Dawson compounds

ASJC Scopus subject areas

  • Inorganic Chemistry

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