Synthesis, structure, and spectroscopy of two ternary uranium(IV) thiophosphates: UP2S9 and UP2S7 containing P2S9 2- and P2S 7 2- ligands

Jean Marie Babo, Laurent Jouffret, Jian Lin, Eric Villa, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The two ternary uranium thiophosphate compounds were isolated from polychalcogenide flux reactions. UP2S9 crystallizes in the tetragonal space group P42/mcm with two formula units per unit cell, where a = 7.762(1) and c = 9.691(3) Å. UP2S7 crystallizes in the orthorhombic space group Fddd with 16 formula units per unit cell, here a = 8.919(3), b = 15.198(4), and c = 30.104(9) Å. Both compounds were characterized through single crystal X-ray, UV-vis-NIR, and Raman spectroscopy. The structures of the two compounds are formed from [US 6]8- chains connected to each other by either the tridentate-chelating P2S9 4- in UP 2S9 or the P2S7 4- in UP2S7 resulting in 3D frameworks. These two ligands have different geometries, but they exhibit similar coordination modes, comparable to the ethane-like P2S6 4-. The uranium cations in both compounds can be assigned an unambiguous oxidation state of +4. The two compounds are semiconductors with nearly identical band-gaps of 1.41 eV.

Original languageEnglish
Pages (from-to)7747-7751
Number of pages5
JournalInorganic Chemistry
Volume52
Issue number13
DOIs
StatePublished - Jul 1 2013
Externally publishedYes

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Uranium compounds
Uranium
Ethane
Chelation
uranium
Raman spectroscopy
Cations
Energy gap
Single crystals
Spectroscopy
Semiconductor materials
uranium compounds
Fluxes
Ligands
X rays
Oxidation
ligands
Geometry
synthesis
cells

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Synthesis, structure, and spectroscopy of two ternary uranium(IV) thiophosphates : UP2S9 and UP2S7 containing P2S9 2- and P2S 7 2- ligands. / Babo, Jean Marie; Jouffret, Laurent; Lin, Jian; Villa, Eric; Albrecht-Schmitt, Thomas E.

In: Inorganic Chemistry, Vol. 52, No. 13, 01.07.2013, p. 7747-7751.

Research output: Contribution to journalArticle

Babo, Jean Marie ; Jouffret, Laurent ; Lin, Jian ; Villa, Eric ; Albrecht-Schmitt, Thomas E. / Synthesis, structure, and spectroscopy of two ternary uranium(IV) thiophosphates : UP2S9 and UP2S7 containing P2S9 2- and P2S 7 2- ligands. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 13. pp. 7747-7751.
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abstract = "The two ternary uranium thiophosphate compounds were isolated from polychalcogenide flux reactions. UP2S9 crystallizes in the tetragonal space group P42/mcm with two formula units per unit cell, where a = 7.762(1) and c = 9.691(3) {\AA}. UP2S7 crystallizes in the orthorhombic space group Fddd with 16 formula units per unit cell, here a = 8.919(3), b = 15.198(4), and c = 30.104(9) {\AA}. Both compounds were characterized through single crystal X-ray, UV-vis-NIR, and Raman spectroscopy. The structures of the two compounds are formed from [US 6]8- chains connected to each other by either the tridentate-chelating P2S9 4- in UP 2S9 or the P2S7 4- in UP2S7 resulting in 3D frameworks. These two ligands have different geometries, but they exhibit similar coordination modes, comparable to the ethane-like P2S6 4-. The uranium cations in both compounds can be assigned an unambiguous oxidation state of +4. The two compounds are semiconductors with nearly identical band-gaps of 1.41 eV.",
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