title: 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?
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, P(2)S(5), and S at 600-700 degrees C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS(6) structure type in the tetragonal space group I$\bar 4$2d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb(2)P(2)S(12), a=15.887(3) and c=13.132(3) A for RbNb(2)P(2)S(12), and a=15.850(2) and c=13.119(3) A for KNb(2)P(2)S(12). Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb(2)S(12)] cluster units and [PS(4)] 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 (31)P 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, CsNb(2)P(2)S(12) may be considered a chalcogenide analogue of metal phosphate bronzes.
authors.affiliation: Institut für Anorganische Chemie und Analytische Chemie der Johannes Gutenberg-Universität, Duesbergweg 10-14, 55099 Mainz, Germany.
authors.forename: Christine
authors.initials: C
authors.lastname: Gieck
authors.forename: Volkmar
authors.initials: V
authors.lastname: Derstroff
authors.forename: Thomas
authors.initials: T
authors.lastname: Block
authors.forename: Claudia
authors.initials: C
authors.lastname: Felser
authors.forename: Guido
authors.initials: G
authors.lastname: Regelsky
authors.forename: Ove
authors.initials: O
authors.lastname: Jepsen
authors.forename: Vadim
authors.initials: V
authors.lastname: Ksenofontov
authors.forename: Philipp
authors.initials: P
authors.lastname: Gütlich
authors.forename: Hellmut
authors.initials: H
authors.lastname: Eckert
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Tremel