title: Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions.
abstract: 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 [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] 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.
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Kuhn
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Leslie M
authors.initials: LM
authors.lastname: Schoop
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Roland
authors.initials: R
authors.lastname: Eger
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Igor
authors.initials: I
authors.lastname: Moudrakovski
authors.affiliation: Institute for Mineralogy, Crystallography and Materials Science, Leipzig University , Scharnhorststraße 20, 04275 Leipzig, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Schwarzmüller
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Viola
authors.initials: V
authors.lastname: Duppel
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.
authors.forename: Reinhard K
authors.initials: RK
authors.lastname: Kremer
authors.affiliation: Institute for Mineralogy, Crystallography and Materials Science, Leipzig University , Scharnhorststraße 20, 04275 Leipzig, Germany.
authors.forename: Oliver
authors.initials: O
authors.lastname: Oeckler
authors.affiliation: Max Planck Institute for Solid State Research , Heisenbergstraße 1, 70569 Stuttgart, Germany.|Department of Chemistry, Ludwig-Maximilians-Universität München , Butenandtstraße 5-13, 81377 München, Germany.|Nanosystems Initiative Munich (NIM) & Center for Nanoscience , Schellingstraße 4, 80799 München, Germany.
authors.forename: Bettina V
authors.initials: BV
authors.lastname: Lotsch
mesh_terms: D000838:Anions / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry; D012643:Selenium / Q000737:chemistry
chemical_list: D000838:Anions; D009942:Organometallic Compounds; D010710:Phosphates; D003300:Copper; D012643:Selenium