NaPdPS4 and RbPdPS4: Systems with infinite straight 1/∞ [PdPS4]- chains soluble in polar solvents and the structure of cubic RbPdPS4{Rb0.33P0.4S 2.23Ox}

Servane Coste, Jason Hanko, Martine Bujoli-Doeuff, Guy Louarn, Michel Evain, Raymond Brec, Bruno Alonso, Stéphane Jobic, Mercouri G. Kanatzidis

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Abstract

The synthesis, crystal structures, chemical and spectroscopic properties of NaPdPS4, RbPdPS4, and RbPdPS4{Rb 0.33P0.4S2.23Ox} are described. NaPdPS4, RbPdPS4, are isostructural and crystallize in the tetragonal system I4/mcm with cell parameters a=7.3074(8)Å, c=12.2308(14)Å and a=8.2954(3)Å, c=12.2284(4)Å respectively. RbPdPS4{Rb0.33P0.4S2.23O x} is cubic, space group Pm-3n and a=12.0042(2)Å. All compounds contain the same 1∞[PdPS4]- chains made of alternating square planar Pd2+ cations and tetrahedral [PS 4]3- anions. RbPdPS4{Rb0.33P 0.4S2.23Ox} contains co-crystallized highly disordered molecular species encapsulated within [Rb8] cubic cavities. Spectroscopic solid state 31P NMR, infrared and Raman data as well as elemental analysis suggest that these species could be S n2- (n=3 or 4) anions and possibly cationic [P 4S6O]6+ fragments. NaPdPS4 and RbPdPS4 exhibit exfoliative dissolution in polar solvents giving rise to solutions that show signs of complex fluid behavior.

Original languageEnglish
Pages (from-to)133-145
Number of pages13
JournalJournal of Solid State Chemistry
Volume175
Issue number2
DOIs
Publication statusPublished - Nov 2003

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Keywords

  • Chain-like materials
  • Complex fluid
  • Exfoliation
  • IR and Raman spectroscopies
  • P NMR
  • Palladium
  • Thiophosphates
  • X-ray diffraction

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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