期刊
JOURNAL OF SOLID STATE CHEMISTRY
卷 175, 期 2, 页码 133-145出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/S0022-4596(03)00138-5
关键词
chain-like materials; thiophosphates; palladium; X-ray diffraction; P-31 NMR; IR and Raman spectroscopies; complex fluid; exfoliation
The synthesis, crystal structures, chemical and spectroscopic properties of NaPdPS4, RbPdPS4, and RbPdPS4{Rb0.33P0.4S2.23Ox} are described. NaPdPS4, RbPdPS4, are isostructural and crystallize in the tetragonal system 14/mcm with cell parameters a = 7.3074(8) Angstrom, c = 12.2308(14) Angstrom and a = 8.2954(3) Angstrom, c = 12.2284(4) Angstrom respectively. RbPdPS4{Rb0.33P0.4S2.23Ox} is cubic, space group Pm-3n and a = 12.0042(2) Angstrom. All compounds contain the same 1/infinity[PdPS4](-) chains made of alternating square planar Pd2+ cations and tetrahedral [PS4](3-) anions. RbPdPS4{Rb0.33P0.4S2.23Ox} contains co-crystallized highly disordered molecular species encapsulated within [Rb-8] cubic cavities. Spectroscopic solid state P-31 NMR, infrared and Raman data as well as elemental analysis suggest that these species could be S-n(2-)(n = 3 or 4) anions and possibly cationic [P4S6O](6+) fragments. NaPdPS4 and RbPdPS4 exhibit exfoliative dissolution in polar solvents giving rise to solutions that show signs of complex fluid behavior. (C) 2003 Elsevier Inc. All rights reserved.
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