2 research outputs found
Structural Stability Diagram of ALnP<sub>2</sub>S<sub>6</sub> Compounds (A = Na, K, Rb, Cs; Ln = Lanthanide)
Thiophosphate
compounds have been studied extensively in the past
for their rich structural variations and for a large variety of interesting
properties. Here, we report 11 new phases with the composition ALnP<sub>2</sub>S<sub>6</sub> (A = Na, K, Rb, Cs; Ln = lanthanide). These
new thiophosphates crystallize in four different structure types,
with the space groups <i>Fdd</i>2, <i>P</i>1Ì…, <i>P</i>2<sub>1</sub>, and <i>P</i>2<sub>1</sub>/<i>c</i>, respectively. All phases are insulating and the calculated
band gaps range between 3 eV and 3.5 eV. Magnetic measurements on
the compounds with open f-shells show paramagnetic behavior and magnetic
moments that match the expected free ion values of the respective
lanthanide cations. We present a structural stability phase diagram
for the ALnP<sub>2</sub>S<sub>6</sub> family of compounds, which reveals
a clear relationship between ionic radii and the preferred crystal
structure, as well as stability regions to form ALnP<sub>2</sub>S<sub>6</sub>-type phases
Copper Selenidophosphates Cu<sub>4</sub>P<sub>2</sub>Se<sub>6</sub>, Cu<sub>4</sub>P<sub>3</sub>Se<sub>4</sub>, Cu<sub>4</sub>P<sub>4</sub>Se<sub>3</sub>, and CuP<sub>2</sub>Se, Featuring Zero‑, One‑, and Two-Dimensional Anions
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 Cu<sub>4</sub>P<sub>2</sub>Se<sub>6</sub> featuring the well-known hexaÂselenidoÂhypodiphosphateÂ(IV)
ion, there are three copper selenidophosphates with low-valent P:
Cu<sub>4</sub>P<sub>3</sub>Se<sub>4</sub> contains two different new
anions, (i) a monomeric (zero-dimensional) selenidophosphate anion
[P<sub>2</sub>Se<sub>4</sub>]<sup>4–</sup> and (ii) a one-dimensional
selenidophosphate anion [P(−Se)]−∞1, which is related to the well-known gray-Se-like [P]−∞1 Zintl anion. Cu<sub>4</sub>P<sub>4</sub>Se<sub>3</sub> contains one-dimensional [P4(−Se)2]2−∞1 polyanions, whereas CuP<sub>2</sub>Se contains the 2D selenidophosphate [P2(−Se)]−∞2 polyanion. It consists
of charge-neutral CuP<sub>2</sub>Se layers separated by a van der
Waals gap which is very rare for a Zintl-type phase. Hence, besides
black P, CuP<sub>2</sub>Se 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