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Kuhn, Alexander; Schoop, Leslie M.; Eger, Roland; Moudrakovski, Igor; Schwarzmüller, Stefan; Duppel, Viola; Kremer, Reinhard K.; Oeckler, Oliver; Lotsch, Bettina V. (2016): Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions. In: Inorganic Chemistry, Vol. 55, No. 16: pp. 8031-8040
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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 hexaselenidohpodiphosphate(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 (1)(infinity)[P(-Se)](-), which is related to the well-known gray-Se-like (1)(infinity)[P](-) Zintl anion. Cu4P4Se3 contains one-dimensional (1)(infinity)[P-4(Se)(2)](2-) polyanions, whereas CuP2Se contains the 2D selenidophosphate (2)(infinity)[P-2(Se)](-) polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare fora 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.