Surfactant-templated inorganic lamellar and non-lamellar hybrid phases containing adamantane [Ge4Se10]4- anions

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Abstract

The metathesis reaction of K4Ge4Se10 with various alkyl tri- and dimethylammonium halides [C(n)H(2n + 1)N(CH3)(3-m)H(m)]X (n = 8, 9, 10, 12, 14, 16, 18; m = 0, 1; X = Cl, Br) led to several new surfactant-inorganic template phases containing selenogermanate adamantane units [Ge4Se10].4- The crystal structures of phases with shorter alkylammonium chains (n = 8 and 9) have been determined by single-crystal X-ray crystallography; octyltrimethylammonium decaselenotetragermanate, [n-C8H17N(CH3)3]4Ge4Se10 (C8-GeSe), monoclinic, space group C2/c, Z = 4, a = 34.2324(9) Å, b = 10.9213(3) Å, c = 19.2700(5) Å, β = 104.567°; nonyltrimethylammonium decaselenotetragermanate [n-C9H19N(CH3)3]4Ge4Se10 (C9-GeSe), triclinic, space group P1, Z = 2, a = 10.7799(2) Å, b = 18.1172(3) Å, c = 19.0075(1) Å, α = 91,881(1)°, β = 90.017(1)°, γ = 98.767(1)°; octyldimethylammonium decaselenotetragermanate [n-C8H17N(CH3)2H]4Ge4Se10 (ODA-GeSe) tetragonal, space group I1/a, Z = 4, a = 18.6462-(1) Å, c = 19.2038(1) Å. C8-GeSe and C9-GeSe are composed of parallel layers of [Ge4Se10]4- anions in a pseudohexagonal arrangement, separated by the charge-balancing surfactant cations. While C9-GeSe contains bilayers of parallel interdigitating surfactant hydrocarbon chains, the shorter chains in C8-GeSe show a crisscross-like arrangement. The presence of hydrogen bonds in ODA-GeSe leads to the formation of a novel nonlamellar phase with isolated adamantane clusters whereby each is surrounded by four surfactant molecules. At the inorganic-organic interface, the Se···H contacts of the surfactant cations to the terminal Se atoms (Se(t)) of the adamantane cluster are unusually short (2.38(5)A), leading to strong N-H···Se hydrogen bonds. [(n-C4H9)3NH]4Ge4Se10 has a very similar arrangement of the organic/inorganic building units to that of ODA-GeSe, including the strong N-H···Se hydrogen bonds.

Original languageEnglish
Pages (from-to)2914-2923
Number of pages10
JournalChemistry of Materials
Volume12
Issue number10
DOIs
Publication statusPublished - 2000

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Adamantane
Surface-Active Agents
Anions
Surface active agents
Negative ions
Hydrogen bonds
Cations
Positive ions
X ray crystallography
Hydrocarbons
Crystal structure
Single crystals
Atoms
Molecules

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

Surfactant-templated inorganic lamellar and non-lamellar hybrid phases containing adamantane [Ge4Se10]4- anions. / Wachhold, M.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 12, No. 10, 2000, p. 2914-2923.

Research output: Contribution to journalArticle

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title = "Surfactant-templated inorganic lamellar and non-lamellar hybrid phases containing adamantane [Ge4Se10]4- anions",
abstract = "The metathesis reaction of K4Ge4Se10 with various alkyl tri- and dimethylammonium halides [C(n)H(2n + 1)N(CH3)(3-m)H(m)]X (n = 8, 9, 10, 12, 14, 16, 18; m = 0, 1; X = Cl, Br) led to several new surfactant-inorganic template phases containing selenogermanate adamantane units [Ge4Se10].4- The crystal structures of phases with shorter alkylammonium chains (n = 8 and 9) have been determined by single-crystal X-ray crystallography; octyltrimethylammonium decaselenotetragermanate, [n-C8H17N(CH3)3]4Ge4Se10 (C8-GeSe), monoclinic, space group C2/c, Z = 4, a = 34.2324(9) {\AA}, b = 10.9213(3) {\AA}, c = 19.2700(5) {\AA}, β = 104.567°; nonyltrimethylammonium decaselenotetragermanate [n-C9H19N(CH3)3]4Ge4Se10 (C9-GeSe), triclinic, space group P1, Z = 2, a = 10.7799(2) {\AA}, b = 18.1172(3) {\AA}, c = 19.0075(1) {\AA}, α = 91,881(1)°, β = 90.017(1)°, γ = 98.767(1)°; octyldimethylammonium decaselenotetragermanate [n-C8H17N(CH3)2H]4Ge4Se10 (ODA-GeSe) tetragonal, space group I1/a, Z = 4, a = 18.6462-(1) {\AA}, c = 19.2038(1) {\AA}. C8-GeSe and C9-GeSe are composed of parallel layers of [Ge4Se10]4- anions in a pseudohexagonal arrangement, separated by the charge-balancing surfactant cations. While C9-GeSe contains bilayers of parallel interdigitating surfactant hydrocarbon chains, the shorter chains in C8-GeSe show a crisscross-like arrangement. The presence of hydrogen bonds in ODA-GeSe leads to the formation of a novel nonlamellar phase with isolated adamantane clusters whereby each is surrounded by four surfactant molecules. At the inorganic-organic interface, the Se···H contacts of the surfactant cations to the terminal Se atoms (Se(t)) of the adamantane cluster are unusually short (2.38(5)A), leading to strong N-H···Se hydrogen bonds. [(n-C4H9)3NH]4Ge4Se10 has a very similar arrangement of the organic/inorganic building units to that of ODA-GeSe, including the strong N-H···Se hydrogen bonds.",
author = "M. Wachhold and Kanatzidis, {Mercouri G}",
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T1 - Surfactant-templated inorganic lamellar and non-lamellar hybrid phases containing adamantane [Ge4Se10]4- anions

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N2 - The metathesis reaction of K4Ge4Se10 with various alkyl tri- and dimethylammonium halides [C(n)H(2n + 1)N(CH3)(3-m)H(m)]X (n = 8, 9, 10, 12, 14, 16, 18; m = 0, 1; X = Cl, Br) led to several new surfactant-inorganic template phases containing selenogermanate adamantane units [Ge4Se10].4- The crystal structures of phases with shorter alkylammonium chains (n = 8 and 9) have been determined by single-crystal X-ray crystallography; octyltrimethylammonium decaselenotetragermanate, [n-C8H17N(CH3)3]4Ge4Se10 (C8-GeSe), monoclinic, space group C2/c, Z = 4, a = 34.2324(9) Å, b = 10.9213(3) Å, c = 19.2700(5) Å, β = 104.567°; nonyltrimethylammonium decaselenotetragermanate [n-C9H19N(CH3)3]4Ge4Se10 (C9-GeSe), triclinic, space group P1, Z = 2, a = 10.7799(2) Å, b = 18.1172(3) Å, c = 19.0075(1) Å, α = 91,881(1)°, β = 90.017(1)°, γ = 98.767(1)°; octyldimethylammonium decaselenotetragermanate [n-C8H17N(CH3)2H]4Ge4Se10 (ODA-GeSe) tetragonal, space group I1/a, Z = 4, a = 18.6462-(1) Å, c = 19.2038(1) Å. C8-GeSe and C9-GeSe are composed of parallel layers of [Ge4Se10]4- anions in a pseudohexagonal arrangement, separated by the charge-balancing surfactant cations. While C9-GeSe contains bilayers of parallel interdigitating surfactant hydrocarbon chains, the shorter chains in C8-GeSe show a crisscross-like arrangement. The presence of hydrogen bonds in ODA-GeSe leads to the formation of a novel nonlamellar phase with isolated adamantane clusters whereby each is surrounded by four surfactant molecules. At the inorganic-organic interface, the Se···H contacts of the surfactant cations to the terminal Se atoms (Se(t)) of the adamantane cluster are unusually short (2.38(5)A), leading to strong N-H···Se hydrogen bonds. [(n-C4H9)3NH]4Ge4Se10 has a very similar arrangement of the organic/inorganic building units to that of ODA-GeSe, including the strong N-H···Se hydrogen bonds.

AB - The metathesis reaction of K4Ge4Se10 with various alkyl tri- and dimethylammonium halides [C(n)H(2n + 1)N(CH3)(3-m)H(m)]X (n = 8, 9, 10, 12, 14, 16, 18; m = 0, 1; X = Cl, Br) led to several new surfactant-inorganic template phases containing selenogermanate adamantane units [Ge4Se10].4- The crystal structures of phases with shorter alkylammonium chains (n = 8 and 9) have been determined by single-crystal X-ray crystallography; octyltrimethylammonium decaselenotetragermanate, [n-C8H17N(CH3)3]4Ge4Se10 (C8-GeSe), monoclinic, space group C2/c, Z = 4, a = 34.2324(9) Å, b = 10.9213(3) Å, c = 19.2700(5) Å, β = 104.567°; nonyltrimethylammonium decaselenotetragermanate [n-C9H19N(CH3)3]4Ge4Se10 (C9-GeSe), triclinic, space group P1, Z = 2, a = 10.7799(2) Å, b = 18.1172(3) Å, c = 19.0075(1) Å, α = 91,881(1)°, β = 90.017(1)°, γ = 98.767(1)°; octyldimethylammonium decaselenotetragermanate [n-C8H17N(CH3)2H]4Ge4Se10 (ODA-GeSe) tetragonal, space group I1/a, Z = 4, a = 18.6462-(1) Å, c = 19.2038(1) Å. C8-GeSe and C9-GeSe are composed of parallel layers of [Ge4Se10]4- anions in a pseudohexagonal arrangement, separated by the charge-balancing surfactant cations. While C9-GeSe contains bilayers of parallel interdigitating surfactant hydrocarbon chains, the shorter chains in C8-GeSe show a crisscross-like arrangement. The presence of hydrogen bonds in ODA-GeSe leads to the formation of a novel nonlamellar phase with isolated adamantane clusters whereby each is surrounded by four surfactant molecules. At the inorganic-organic interface, the Se···H contacts of the surfactant cations to the terminal Se atoms (Se(t)) of the adamantane cluster are unusually short (2.38(5)A), leading to strong N-H···Se hydrogen bonds. [(n-C4H9)3NH]4Ge4Se10 has a very similar arrangement of the organic/inorganic building units to that of ODA-GeSe, including the strong N-H···Se hydrogen bonds.

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