Chemistry of Gold in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of the Low-Dimensional Compounds A3AuP2Se8 (A = K, Rb, Cs), A2Au2P2Se6 (A = K, Rb), A2AuPS4 (A = K, Rb, Cs), and AAuP2S 7(A = K, Rb)

Konstantinos Chondroudis, Jason A. Hanko, Mercouri G. Kanatzidis

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Abstract

The reaction of Au with a molten mixture of A2Q/P2Q5/Q (Q = S, Se) produced the quaternary compounds A3AuP2Se8 (A = K, Rb, Cs) (I-III), A2Au2P2Se6 (A = K, Rb) (IV, V), A2AuPS4 (A = K, Rb, Cs) (VI-VIII), and AAuP2S7 (A = K, Rb) (IX, X). I-III crystallize in the acentric space group Cc (No. 9): I, a = 7.122(2) Å, b = 12.527(3) Å, c = 18.666(4) Å, β= 96.06(2)°, Z = 4. IV and V crystallize in the space group C2lm (No. 12): IV, a = 12.289(2) Å, b = 7.210(1) Å, c = 8.107(1) Å, β= 115.13(1)°, Z = 2. VI and VII crystallize in the space group P21lm (No. 11): VI, a = 6.518(2) Å, b = 6.747(2) Å, c = 9.468(3) Å, β= 92.98(2)°, Z = 2. VIII crystallizes in the space group Pbcm (No. 57) with a = 6.904(3) Å, b = 20.093(6) Å, c = 7.025(5) Å, and Z = 4. IX and X crystallize in the space group C2lc (No. 15): IX, a = 7.917(3) Å, b = 9.247(2) Å, c = 14.968(3) Å, β= 91.84(9)°, Z = 4. Compounds I-III have a one-dimensional structure with [AuP2Se8]n3n- chains separated by A+ cations. The monovalent Au cation is linearly coordinated to the new ligand [P2Se8]4-. IV and V possess a one-dimensional structure with [Au2Se6]n2n- chains separated by A+ ions. The monovalent Au cation is linearly coordinated to ethane like [P2Se6]4- ligands. VI and VII have a one-dimensional structure with [AuPS4]n2n- chains separated by A+ cations. The Au+ cation is linearly coordinated to alternating [PS4]3- tetrahedra. The structure of VIII is related to that of I-III with [AuPS4]n2n- chains. The diselenide of the [P2Se8]4- unit is replaced by a second, essentially linear, S-Au-S linkage leaving the structure of the chain unchanged. IX and X have the [AuP2S7]n- chains with square planar Au3+ centers. The compounds were characterized with differential thermal analysis, far-IR, Raman spectroscopy, solid-state UV/vis diffuse reflectance spectroscopy, and single-crystal optical spectroscopy. Cs2AuPS4, at T > 375 °C, converts to β-Cs2AuPS4, which is isostructural to K2AuPS4.

Original languageEnglish
Pages (from-to)2623-2632
Number of pages10
JournalInorganic Chemistry
Volume36
Issue number12
DOIs
Publication statusPublished - Jan 1 1997

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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