Crystal Structure and Thermodynamic Analysis of the New Semiconducting Chevrel Phase Re6S8Cl2

Re6S8Cl2 single crystals have been synthesized by chemical vapour transport with chlorine as transporting agent. Structure analysis revealed that the material is isomorphous with Re6S8Br2 and Re6Se8Br2 but not with the lamellar Re6Se8Cl2. The thermal stability of this semiconducting rhenium cluster compound was simulated as a function of vapour phase composition by thermochemical calculations in the ternary system Re–S–Cl at temperatures 1000, 1200 and 1400 K. Predominance-area phase diagrams indicate that Re6S8Cl2 can coexist with Re and ReS2 depending on the vapour pressure ratios of S2/S2Cl2 and Cl2/Re3Cl9.

[1]  N. Alonso‐Vante,et al.  Structure and photoelectrochemical properties of semiconducting rhenium cluster chalcogenides: Re6X8Br2 (X S, Se) , 1992 .

[2]  M. Wakihara,et al.  A Rechargeable Lithium Battery Employing Cobalt Chevrel‐Phase Compound as the Cathode , 1991 .

[3]  G. Eriksson,et al.  ChemSage—A computer program for the calculation of complex chemical equilibria , 1990 .

[4]  N. Shekar,et al.  Single crystal growth of CuxMo6Se8 , 1990 .

[5]  N. Alonso‐Vante,et al.  Transition metal cluster materials for multi-electron transfer catalysis , 1989 .

[6]  F. Lévy,et al.  Single Crystal Growth, Structure and Characterization of the Octahedral Cluster Compound Re6Se8Br2 , 1988 .

[7]  C. Lévy‐Clément,et al.  Photoelectrochemical properties of Re6Se8Cl2 a lamellar transition metal cluster compound , 1985 .

[8]  J. Lehn,et al.  Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)3Cl (bipy = 2,2′-bipyridine) , 1984 .

[9]  R. Hoffmann,et al.  Molybdenum Chalcogenides: Clusters, Chains, and Extended Solids. The Approach to Bonding in Three Dimensions , 1983 .

[10]  D. I. Stuart,et al.  An empirical method for correcting diffractometer data for absorption effects , 1983 .

[11]  W. Bronger,et al.  Synthesis and crystal structures of Ba2Re6S11 and Sr2Re6S11, compounds containing [Re6S8] clusters , 1982 .

[12]  G. Krabbes,et al.  Darstellung der supraleitenden ternären Phase PbMo6S8 durch chemischen Transport , 1981 .

[13]  W. Bronger,et al.  Na2Re3S6 und K2Re3S6, zwei thiorhenate mit [Re6S8]-clustern , 1980 .

[14]  H. Jenkins,et al.  Thermochemistry of alkali-metal hexachloro- and hexabromo-tungstates(IV) and -rhenates(IV) , 1979 .

[15]  Ø. Fischer,et al.  Chevrel phases: Superconducting and normal state properties , 1978 .

[16]  L. Mattheiss,et al.  Cluster model for the electronic structure of the Chevrel-phase compound PbMo6S8 , 1977 .

[17]  R. Flukiger,et al.  Metallurgical and physical properties of ternary Molybdenum Sulfides (M x Mo 3 S 4 ) as synthetized in the bulk state , 1977 .

[18]  A. Büchler,et al.  The Vaporization of Rhenium Trichloride and Rhenium Tribromide1 , 1966 .