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
Publication statusPublished - 1997

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Alkali Metals
Gold
alkali metals
Cations
Molten materials
chemistry
gold
Fluxes
cations
synthesis
Ligands
Ethane
ligands
Differential thermal analysis
Raman spectroscopy
linkages
tetrahedrons
ethane
spectroscopy
Single crystals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{c8d5568172e54f079864f5439a21de22,
title = "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)",
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) {\AA}, b = 12.527(3) {\AA}, c = 18.666(4) {\AA}, β= 96.06(2)°, Z = 4. IV and V crystallize in the space group C2lm (No. 12): IV, a = 12.289(2) {\AA}, b = 7.210(1) {\AA}, c = 8.107(1) {\AA}, β= 115.13(1)°, Z = 2. VI and VII crystallize in the space group P21lm (No. 11): VI, a = 6.518(2) {\AA}, b = 6.747(2) {\AA}, c = 9.468(3) {\AA}, β= 92.98(2)°, Z = 2. VIII crystallizes in the space group Pbcm (No. 57) with a = 6.904(3) {\AA}, b = 20.093(6) {\AA}, c = 7.025(5) {\AA}, and Z = 4. IX and X crystallize in the space group C2lc (No. 15): IX, a = 7.917(3) {\AA}, b = 9.247(2) {\AA}, c = 14.968(3) {\AA}, 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.",
author = "Konstantinos Chondroudis and Hanko, {Jason A.} and Kanatzidis, {Mercouri G}",
year = "1997",
language = "English",
volume = "36",
pages = "2623--2632",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - 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)

AU - Chondroudis, Konstantinos

AU - Hanko, Jason A.

AU - Kanatzidis, Mercouri G

PY - 1997

Y1 - 1997

N2 - 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.

AB - 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.

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M3 - Article

VL - 36

SP - 2623

EP - 2632

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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