Reactivity of copper in molten polytelluride salts. K4Cu8Te11, A3Cu8Te10 (A = Rb, Cs), AA′2Cu8Te10 (A, A′ = K, Rb, Cs), and A2BaCu8Te10 (A = K, Rb, Cs): Novel solids based on endohedrally occupied [Cu8Te12] dodecahedral cage-clusters

Xiang Zhang, Younbong Park, Mercouri G Kanatzidis, Jon L. Schindler, Carl R. Kannewurf, Seeyearl Seong, Thomas Albright, Mercouri G. Kanatzidis

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Abstract

The reaction of copper with molten alkali polytelluride salts led to several novel compounds with a characteristic structural feature based on a pentagonal dodecahedral geometric solid. We report here in detail the synthesis, structure, and chemical, spectroscopic, and charge-transport properties of K4Cu8Te11, A3Cu8Te10, and A2BaCu8Te10 along with electronic band structure calculations on the two-dimensional Cu8Te10 framework. K4Cu8Te11 is monoclinic C2/m with a = 24.086(3) Å, b = 6.821(6) Å, c = 18.461(3) Å, β= 124.45(1)°, V = 2501 Å3 at 23 °C, Z = 4, no. of data used (I > 3σ(I)) 2029, no. of variables 121. The final R/RW was 2.5%/3.7%. Rb3Cu8Te10 is monoclinic C2/m with a = 24.420(11) Å, b = 6.974(6) Å, c = 6.933(1) Å, β= 104.90(1)°, V = 1141 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 721, no. of variables, 57 final R/Rw 5.7%/7.3%. Cs3Cu8Te10 is orthorhombic Immm with a = 7.053(2) Å, b = 24.159(3) Å, c = 6.935(3) Å, V = 1182 Å3 at 23 °C, Z= 2, no. of data used (I > 3σ(I)) 839, no. of variables 36 final R/RW 3.2%/5.0%. K0.9Cs2.1Cu8Te10 is orthorhombic Immm with a = 7.023(3) Å, b = 23.895(6) Å, c = 6.908(3) Å, V = 1159 Å3 at 23 °C, Z = 2 no. of data used (I > 3σ(I)) 625, no. of variables 37, final R/RW 3.5%/3.0%. K2BaCu8Te10 is monoclinic C2/m with a = 23.245(5) Å, b = 6.950(5) Å, c = 7.061(5) Å, β= 101.23(4)°, V = 1119 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 1445, no. of variables 57, final R/Rw 8.8%/11.3%. Cs2BaCu8Te10 is orthorhombic Immm with a = 7.109(2) Å, b = 23.761(16) Å, c = 6.966(3) Å, V = 1177 Å3 and Z = 2, no. of data used (I > 3σ(I)) 795, no. of variables 35, final R/Rw 3.0%/6.0%. All compounds reported here, except K4Cu8Te11, contain the same layered Cu/Te framework built from the [Cu8Te12] pentagonal dodecahedral cage-cluster. This characteristic cluster, however, is also the building block of the three-dimensional structure of K4Cu8Te11. The structure consists of condensed pentagonal dodecahedral Cu8(Te2)6 clusters sharing Te-Te edges. Each Cu8(Te2)6 dodecahedral cluster encapsulates an alkali or a Ba2+ ion. The A3Cu8Te10 are mixed valence compounds and exhibit metallic properties as demonstrated by electrical conductivity, thermoelectric power, and magnetic susceptibility measurements. K4Cu8Te11 and A2BaCu8Te10 are electron-precise semiconductors with narrow band gaps. Extended-Hiickel theoretical tight binding calculations on A3Cu8Te10 confirm the metallic nature of the materials.

Original languageEnglish
Pages (from-to)10300-10310
Number of pages11
JournalJournal of the American Chemical Society
Volume117
Issue number41
Publication statusPublished - Oct 18 1995

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Alkalies
Molten materials
Copper
Salts
Electric Conductivity
Semiconductors
Thermoelectric power
Magnetic susceptibility
Band structure
Transport properties
Charge transfer
Energy gap
Electrons
Ions
Semiconductor materials

ASJC Scopus subject areas

  • Chemistry(all)

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Reactivity of copper in molten polytelluride salts. K4Cu8Te11, A3Cu8Te10 (A = Rb, Cs), AA′2Cu8Te10 (A, A′ = K, Rb, Cs), and A2BaCu8Te10 (A = K, Rb, Cs) : Novel solids based on endohedrally occupied [Cu8Te12] dodecahedral cage-clusters. / Zhang, Xiang; Park, Younbong; Kanatzidis, Mercouri G; Schindler, Jon L.; Kannewurf, Carl R.; Seong, Seeyearl; Albright, Thomas; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 117, No. 41, 18.10.1995, p. 10300-10310.

Research output: Contribution to journalArticle

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title = "Reactivity of copper in molten polytelluride salts. K4Cu8Te11, A3Cu8Te10 (A = Rb, Cs), AA′2Cu8Te10 (A, A′ = K, Rb, Cs), and A2BaCu8Te10 (A = K, Rb, Cs): Novel solids based on endohedrally occupied [Cu8Te12] dodecahedral cage-clusters",
abstract = "The reaction of copper with molten alkali polytelluride salts led to several novel compounds with a characteristic structural feature based on a pentagonal dodecahedral geometric solid. We report here in detail the synthesis, structure, and chemical, spectroscopic, and charge-transport properties of K4Cu8Te11, A3Cu8Te10, and A2BaCu8Te10 along with electronic band structure calculations on the two-dimensional Cu8Te10 framework. K4Cu8Te11 is monoclinic C2/m with a = 24.086(3) {\AA}, b = 6.821(6) {\AA}, c = 18.461(3) {\AA}, β= 124.45(1)°, V = 2501 {\AA}3 at 23 °C, Z = 4, no. of data used (I > 3σ(I)) 2029, no. of variables 121. The final R/RW was 2.5{\%}/3.7{\%}. Rb3Cu8Te10 is monoclinic C2/m with a = 24.420(11) {\AA}, b = 6.974(6) {\AA}, c = 6.933(1) {\AA}, β= 104.90(1)°, V = 1141 {\AA}3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 721, no. of variables, 57 final R/Rw 5.7{\%}/7.3{\%}. Cs3Cu8Te10 is orthorhombic Immm with a = 7.053(2) {\AA}, b = 24.159(3) {\AA}, c = 6.935(3) {\AA}, V = 1182 {\AA}3 at 23 °C, Z= 2, no. of data used (I > 3σ(I)) 839, no. of variables 36 final R/RW 3.2{\%}/5.0{\%}. K0.9Cs2.1Cu8Te10 is orthorhombic Immm with a = 7.023(3) {\AA}, b = 23.895(6) {\AA}, c = 6.908(3) {\AA}, V = 1159 {\AA}3 at 23 °C, Z = 2 no. of data used (I > 3σ(I)) 625, no. of variables 37, final R/RW 3.5{\%}/3.0{\%}. K2BaCu8Te10 is monoclinic C2/m with a = 23.245(5) {\AA}, b = 6.950(5) {\AA}, c = 7.061(5) {\AA}, β= 101.23(4)°, V = 1119 {\AA}3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 1445, no. of variables 57, final R/Rw 8.8{\%}/11.3{\%}. Cs2BaCu8Te10 is orthorhombic Immm with a = 7.109(2) {\AA}, b = 23.761(16) {\AA}, c = 6.966(3) {\AA}, V = 1177 {\AA}3 and Z = 2, no. of data used (I > 3σ(I)) 795, no. of variables 35, final R/Rw 3.0{\%}/6.0{\%}. All compounds reported here, except K4Cu8Te11, contain the same layered Cu/Te framework built from the [Cu8Te12] pentagonal dodecahedral cage-cluster. This characteristic cluster, however, is also the building block of the three-dimensional structure of K4Cu8Te11. The structure consists of condensed pentagonal dodecahedral Cu8(Te2)6 clusters sharing Te-Te edges. Each Cu8(Te2)6 dodecahedral cluster encapsulates an alkali or a Ba2+ ion. The A3Cu8Te10 are mixed valence compounds and exhibit metallic properties as demonstrated by electrical conductivity, thermoelectric power, and magnetic susceptibility measurements. K4Cu8Te11 and A2BaCu8Te10 are electron-precise semiconductors with narrow band gaps. Extended-Hiickel theoretical tight binding calculations on A3Cu8Te10 confirm the metallic nature of the materials.",
author = "Xiang Zhang and Younbong Park and Kanatzidis, {Mercouri G} and Schindler, {Jon L.} and Kannewurf, {Carl R.} and Seeyearl Seong and Thomas Albright and Kanatzidis, {Mercouri G.}",
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TY - JOUR

T1 - Reactivity of copper in molten polytelluride salts. K4Cu8Te11, A3Cu8Te10 (A = Rb, Cs), AA′2Cu8Te10 (A, A′ = K, Rb, Cs), and A2BaCu8Te10 (A = K, Rb, Cs)

T2 - Novel solids based on endohedrally occupied [Cu8Te12] dodecahedral cage-clusters

AU - Zhang, Xiang

AU - Park, Younbong

AU - Kanatzidis, Mercouri G

AU - Schindler, Jon L.

AU - Kannewurf, Carl R.

AU - Seong, Seeyearl

AU - Albright, Thomas

AU - Kanatzidis, Mercouri G.

PY - 1995/10/18

Y1 - 1995/10/18

N2 - The reaction of copper with molten alkali polytelluride salts led to several novel compounds with a characteristic structural feature based on a pentagonal dodecahedral geometric solid. We report here in detail the synthesis, structure, and chemical, spectroscopic, and charge-transport properties of K4Cu8Te11, A3Cu8Te10, and A2BaCu8Te10 along with electronic band structure calculations on the two-dimensional Cu8Te10 framework. K4Cu8Te11 is monoclinic C2/m with a = 24.086(3) Å, b = 6.821(6) Å, c = 18.461(3) Å, β= 124.45(1)°, V = 2501 Å3 at 23 °C, Z = 4, no. of data used (I > 3σ(I)) 2029, no. of variables 121. The final R/RW was 2.5%/3.7%. Rb3Cu8Te10 is monoclinic C2/m with a = 24.420(11) Å, b = 6.974(6) Å, c = 6.933(1) Å, β= 104.90(1)°, V = 1141 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 721, no. of variables, 57 final R/Rw 5.7%/7.3%. Cs3Cu8Te10 is orthorhombic Immm with a = 7.053(2) Å, b = 24.159(3) Å, c = 6.935(3) Å, V = 1182 Å3 at 23 °C, Z= 2, no. of data used (I > 3σ(I)) 839, no. of variables 36 final R/RW 3.2%/5.0%. K0.9Cs2.1Cu8Te10 is orthorhombic Immm with a = 7.023(3) Å, b = 23.895(6) Å, c = 6.908(3) Å, V = 1159 Å3 at 23 °C, Z = 2 no. of data used (I > 3σ(I)) 625, no. of variables 37, final R/RW 3.5%/3.0%. K2BaCu8Te10 is monoclinic C2/m with a = 23.245(5) Å, b = 6.950(5) Å, c = 7.061(5) Å, β= 101.23(4)°, V = 1119 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 1445, no. of variables 57, final R/Rw 8.8%/11.3%. Cs2BaCu8Te10 is orthorhombic Immm with a = 7.109(2) Å, b = 23.761(16) Å, c = 6.966(3) Å, V = 1177 Å3 and Z = 2, no. of data used (I > 3σ(I)) 795, no. of variables 35, final R/Rw 3.0%/6.0%. All compounds reported here, except K4Cu8Te11, contain the same layered Cu/Te framework built from the [Cu8Te12] pentagonal dodecahedral cage-cluster. This characteristic cluster, however, is also the building block of the three-dimensional structure of K4Cu8Te11. The structure consists of condensed pentagonal dodecahedral Cu8(Te2)6 clusters sharing Te-Te edges. Each Cu8(Te2)6 dodecahedral cluster encapsulates an alkali or a Ba2+ ion. The A3Cu8Te10 are mixed valence compounds and exhibit metallic properties as demonstrated by electrical conductivity, thermoelectric power, and magnetic susceptibility measurements. K4Cu8Te11 and A2BaCu8Te10 are electron-precise semiconductors with narrow band gaps. Extended-Hiickel theoretical tight binding calculations on A3Cu8Te10 confirm the metallic nature of the materials.

AB - The reaction of copper with molten alkali polytelluride salts led to several novel compounds with a characteristic structural feature based on a pentagonal dodecahedral geometric solid. We report here in detail the synthesis, structure, and chemical, spectroscopic, and charge-transport properties of K4Cu8Te11, A3Cu8Te10, and A2BaCu8Te10 along with electronic band structure calculations on the two-dimensional Cu8Te10 framework. K4Cu8Te11 is monoclinic C2/m with a = 24.086(3) Å, b = 6.821(6) Å, c = 18.461(3) Å, β= 124.45(1)°, V = 2501 Å3 at 23 °C, Z = 4, no. of data used (I > 3σ(I)) 2029, no. of variables 121. The final R/RW was 2.5%/3.7%. Rb3Cu8Te10 is monoclinic C2/m with a = 24.420(11) Å, b = 6.974(6) Å, c = 6.933(1) Å, β= 104.90(1)°, V = 1141 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 721, no. of variables, 57 final R/Rw 5.7%/7.3%. Cs3Cu8Te10 is orthorhombic Immm with a = 7.053(2) Å, b = 24.159(3) Å, c = 6.935(3) Å, V = 1182 Å3 at 23 °C, Z= 2, no. of data used (I > 3σ(I)) 839, no. of variables 36 final R/RW 3.2%/5.0%. K0.9Cs2.1Cu8Te10 is orthorhombic Immm with a = 7.023(3) Å, b = 23.895(6) Å, c = 6.908(3) Å, V = 1159 Å3 at 23 °C, Z = 2 no. of data used (I > 3σ(I)) 625, no. of variables 37, final R/RW 3.5%/3.0%. K2BaCu8Te10 is monoclinic C2/m with a = 23.245(5) Å, b = 6.950(5) Å, c = 7.061(5) Å, β= 101.23(4)°, V = 1119 Å3 at 23 °C, Z = 2, no. of data used (I > 3σ(I)) 1445, no. of variables 57, final R/Rw 8.8%/11.3%. Cs2BaCu8Te10 is orthorhombic Immm with a = 7.109(2) Å, b = 23.761(16) Å, c = 6.966(3) Å, V = 1177 Å3 and Z = 2, no. of data used (I > 3σ(I)) 795, no. of variables 35, final R/Rw 3.0%/6.0%. All compounds reported here, except K4Cu8Te11, contain the same layered Cu/Te framework built from the [Cu8Te12] pentagonal dodecahedral cage-cluster. This characteristic cluster, however, is also the building block of the three-dimensional structure of K4Cu8Te11. The structure consists of condensed pentagonal dodecahedral Cu8(Te2)6 clusters sharing Te-Te edges. Each Cu8(Te2)6 dodecahedral cluster encapsulates an alkali or a Ba2+ ion. The A3Cu8Te10 are mixed valence compounds and exhibit metallic properties as demonstrated by electrical conductivity, thermoelectric power, and magnetic susceptibility measurements. K4Cu8Te11 and A2BaCu8Te10 are electron-precise semiconductors with narrow band gaps. Extended-Hiickel theoretical tight binding calculations on A3Cu8Te10 confirm the metallic nature of the materials.

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