From semi-metal to superconductor: The New Mo12 Cluster Sulfides Rb1+xMo12S14 (x = 0.08, and 1.65) - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Journal of Alloys and Compounds Année : 2021

From semi-metal to superconductor: The New Mo12 Cluster Sulfides Rb1+xMo12S14 (x = 0.08, and 1.65)

Résumé

The novel Mo12 cluster sulfides Rb2.65Mo12S14 have been synthesized by direct solid-state reaction at a temperature of about 1500 °C in a welded Mo tubing. The crystal structure of Rb2.65Mo12S14 (space group P-31c: a = 9.2828(6) Å, c = 16.446(5) Å) was solved from X-ray single-crystal data. It is isomorphous with the K1+xMo12S14 compounds in which x ranges from 0 to 1.6. Consequently, the Mo-S network presents interconnected Mo12S14 cluster units delimiting large tunnels that are randomly occupied by a part of the Rb+ ions, the other ones being localized in large voids between two consecutive Mo12S14 units along the [001] direction. By topochemical redox reactions at around 90 °C, we could remove a part of the Rb+ ions from the channels and thus, form the oxidized phase Rb1.08Mo12S14. Electrical resistivity measurements performed on single crystals of Rb2.65Mo12S14 and Rb1.08Mo12S14 shows that the oxidized form is a semimetal while the reduced form is a metal and becomes superconducting below 4.07 K. The evolution of Mo-Mo bond lengths within the trioctahedral Mo12 cluster with respect to the cationic charge x is discussed and, compared with that found in the potassium series.
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Dates et versions

hal-03225466 , version 1 (10-06-2021)

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Patrick Gougeon, Philippe Gall. From semi-metal to superconductor: The New Mo12 Cluster Sulfides Rb1+xMo12S14 (x = 0.08, and 1.65). Journal of Alloys and Compounds, 2021, 872, pp.159595. ⟨10.1016/j.jallcom.2021.159595⟩. ⟨hal-03225466⟩
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