Cu Insertion Into the Mo12 Cluster Compound Cs2Mo12Se14: Synthesis, Crystal and Electronic Structures, and Physical Properties

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• 作者：Rabih Al Rahal Al Orabi ; Bruno Fontaine ; Regis Gautier ; Patrick Gougeon ; Philippe Gall ; Yohan Bouyrie ; Anne Dauscher ; Christophe Candolfi ; Bertrand Lenoir
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 5, 2016
• 年：2016
• 卷：55
• 期：13
• 页码：6616-6624
• 全文大小：567K
• 年卷期：0
• ISSN：1520-510X

文摘

Mo-based cluster compounds are promising materials for high-temperature thermoelectric applications due to their intrinsic, extremely low thermal conductivity values. In this study, polycrystalline cluster compounds Cs₂Cu_xMo₁₂Se₁₄ were prepared for a wide range of Cu contents (0 ≤ x ≤ 2). All samples crystallize isostructurally in the trigonal space group R3̅. The position of the Cu atoms in the unit cell was determined by X-ray diffraction on a single-crystalline specimen indicating that these atoms fill the empty space between the Mo–Se clusters. Density functional theory calculations predict a metallic ground state for all compositions, in good agreement with the experimental findings. Magnetization measurements indicate a rapid suppression of the superconducting state that develops in the x = 0.0 sample upon Cu insertion. Transport properties measurements, performed in a wide temperature range (2–630 K) on the two end-member compounds x = 0 and x = 2, revealed a multiband electrical conduction as shown by sign reversal of the thermopower as a function of temperature.