Konstantinos Chondroudis

Polychalcogenophosphate flux synthesis of 1D-KInP2Se6 and 1D and 3D-NaCrP2S6

Abstract Three new chalcogenophosphates, 1D-KInP 2 Se 6 ( I ), 1D-NaCrP 2 S 6 ( II ) and 3D-NaCrP 2 S 6 ( III ), have been synthesized and their structure determined from single crystal diffraction analysis. ( I ) and ( II ) crystallize in the monoclinic system (space group P2 1 /n, No.xa014) with cell parameters a =7.5112(11), b =6.4861(5), c =22.789(2) A and β =98.912(16)° ( V =1096.9(2)xa0A 3 ), Z =4 and R / Rw ( F 2 )=0.0234/0.0387 (for 900 observed reflections and 92 refined parameters) for ( I ) and a =7.0279(5), b =5.8797(2), c =21.2578(14)xa0A and β =92.110(3)° ( V =877.82(9)xa0A 3 ), Z =4 and R / Rw ( F 2 )=0.0572/0.1151 (for 1455 observed reflections and 92 refined parameters) for ( II ). Both materials exhibit 1 / ∞ [MP 2 Q 6 ] − chains built upon [MQ 6 ] octahedra (M=In, Cr; Q=Se, S) sharing edges to define 1 / ∞ [MQ 4 ] 5− zigzag fibers which are capped by tetradentate ethane-like [P 2 Q 6 ] groups. ( III ) crystallizes in the orthorhombic system (space group Fdd2, No.xa043) with cell parameters a =10.9742(7), b =7.9828(6), c =20.8590(19)xa0A ( V =1827.3(4)xa0A 3 ), Z =8 and R / Rw =0.0184/0.0378 (for 967 observed reflections and 47 refined parameters), and displays a three-dimensional framework arrangement. Its structure is similar to that of TiP 2 S 6 where titanium atoms are substituted for the chromium, the sodium atoms being inserted in the empty tunnels to ensure the charge balance. The exfoliation properties of 1D-NaCrP 2 S 6 in polar solvents are reported.

[Ce(PSe4)4]9−: a highly anionic Ce3+ selenophosphate coordination complex

Abstract The reaction of Ce with the basic polychalcophosphate flux Rb10P4Se25 yielded the quaternary selenophosphate compound Rb9Ce(PSe4)4. The discrete [Ce(PSe4)4]9− anion possesses the highest charge observed in a monometallic complex. The Ce3+ center is chelated by four bidentate [PSe4]3− ligands so it achieves a dodecahedral coordination geometry, and the complex belongs to the dodecahedral sub-class Id (D2d- 4 2m ), according to the Hoard and Silverton notation. The UV–Vis, optical, IR spectroscopic and magnetism data for the compound are reported.

Isolation of [Sn(PSe5)3]5– and [Sn2Se4(PSe5)2]6–; the first discrete complexes from molten alkali-metal polyselenophosphate fluxes

The use of basic polychalcophosphate fluxes yield the quaternary molecular compounds [Sn(PSe5)3]5– and [Sn2Se4(PSe5)2]6–, the first examples of discrete complexes produced from molten fluxes.

[M4(Se2)2(PSe4)4]8-: a novel, tetranuclear, clusteranion with a stellane-like core

The molecular cluster compounds n[M n 4 n(Se n 2 n) n 2 n(PSe n 4 n) n 4 n] n n 8- n (M=Cd, Hg) form by the reaction of Cd and Hg with nbasic polychalcophosphate fluxes.