The ternary alkali selenophosphates KPSe6 and RbPSe6 crystallize in the polar orthorhombic space group Pca21 with a = 11.7764(17) Å, b = 6.8580(10) Å, c = 11.4596(16) Å, and Z = 4 for RbPSe6. CsPSe6 crystallizes in the monoclinic space group P2/n with a = 6.877(3) Å, b = 12.713(4) Å, c = 11.242(4) Å, β = 92.735(7)°, and Z = 4. All compounds feature the one-dimensional infinite chain of [PSe2(Se)4-], where each P atom is connected with Se42- bridge. These compounds show reversible glass-crystal transition, and 31P NMR data suggest that crystallization and infinite [PSe6-] chain formation are coupled processes.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry