Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions

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• 作者：Alexander Kuhn ; Leslie M. Schoop ; Roland Eger ; Igor Moudrakovski ; Stefan Schwarzmüller ; Viola Duppel ; Reinhard K. Kremer ; Oliver Oeckler ; Bettina V. Lotsch
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 15, 2016
• 年：2016
• 卷：55
• 期：16
• 页码：8031-8040
• 全文大小：762K
• 年卷期：0
• ISSN：1520-510X

文摘

Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu₄P₂Se₆ featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu₄P₃Se₄ contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P₂Se₄]^4– and (ii) a one-dimensional selenidophosphate anion , which is related to the well-known gray-Se-like Zintl anion. Cu₄P₄Se₃ contains one-dimensional polyanions, whereas CuP₂Se contains the 2D selenidophosphate polyanion. It consists of charge-neutral CuP₂Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP₂Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.