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  An Inorganic Double Helix Sheathing Alkali Metal Cations: ANb2P2S12 (A=K, Rb, Cs), A Series of Thiophosphates Close to the Metal-Nonmetal Boundary - Chalcogenide Analogues of Transition-Metal Phosphate Bronzes?

Gieck, C., Derstroff, V., Block, T., Felser, C., Regelsky, G., Jepsen, O., et al. (2004). An Inorganic Double Helix Sheathing Alkali Metal Cations: ANb2P2S12 (A=K, Rb, Cs), A Series of Thiophosphates Close to the Metal-Nonmetal Boundary - Chalcogenide Analogues of Transition-Metal Phosphate Bronzes? Chemistry - A European Journal, 10(2), 382-391. doi:10.1002/chem.200103504.

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Gieck, Christine1, Author
Derstroff, Volkmar1, Author
Block, Thomas1, Author
Felser, Claudia2, Author           
Regelsky, Guido1, Author
Jepsen, Ove1, Author
Ksenofontov, Vadim1, Author
Gütlich, Philipp1, Author
Eckert, Hellmut1, Author
Tremel, Wolfgang1, Author
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1external, ou_persistent22              
2External Organizations, ou_persistent22              

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 Abstract: The new quaternary niobium thiophosphates ANb(2)P(2)S(12) (A = K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A(2)S, P2S5, and S at 600-700degreesC in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS6 structure type in the tetragonal space group I (4) over bar 2d with eight formula units per unit cell and lattice constants a = 15.923(2) and c = 13.238(3) Angstrom for CsNb2P2S12, a = 15.887(3) and c = 13.132(3) Angstrom for RbNb2P2S12, and a = 15.850(2) and c = 13.119(3) Angstrom for KNb2P2S12. Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb2S12] cluster units and [PS4] thiophosphate groups. The cavities and tunnels, which are formed by the helical chains, are filled with A(+) ions. Temperature-dependent conductivity studies reveal thermally activated electrical transport behavior. This result is consistent with the observation of a temperature-dependent contribution to the P-31 MAS-NMR shift, suggesting that the delocalized s-electron spin density increases with increasing temperature. These findings are supported by the results of tight-binding band structure calculations which reveal that the unusual electrical transport behavior of ANb(2)P(2)S(12) is a consequence of the structure symmetry. Therefore, CsNb2P2S12 may be considered a chalcogenide analogue of metal phosphate bronzes.

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 Dates: 2004-01-23
 Publication Status: Issued
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 Identifiers: ISI: 000188712200008
DOI: 10.1002/chem.200103504
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Title: Chemistry - A European Journal
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 10 (2) Sequence Number: - Start / End Page: 382 - 391 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058