Thiophosphate Phase Diagrams Developed in Conjunction with the Synthesis of the New Compounds KLaP<sub>2</sub>S<sub>6</sub>, K<sub>2</sub>La(P<sub>2</sub>S<sub>6</sub>)<sub>1/2</sub>(PS<sub>4</sub>), K<sub>3</sub>La(PS<sub>4</sub>)<sub>2</sub>, K<sub>4</sub>La<sub>0.67</sub>(PS<sub>4</sub>)<sub>2</sub>, K<sub>9-</sub><i><sub>x</sub></i>La<sub>1+</sub><i><sub>x</sub></i><sub>/3</sub>(PS<sub>4</sub>)<sub>4</sub> (<i>x</i> = 0.5), K<sub>4</sub>Eu(PS<sub>4</sub>)<sub>2</sub>, and KEuPS<sub>4</sub>
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An alkali-metal sulfur reactive flux has been used to synthesize a series of quaternary rare-earth metal compounds. These include KLaP2S6 (I), K2La(P2S6)1/2(PS4) (II), K3La(PS4)2 (III), K4La0.67(PS4)2 (IV), K9-xLa1+x/3(PS4)4 (x = 0.5) (V), K4Eu(PS4)2 (VI), and KEuPS4 (VII). Compound I crystallizes in the monoclinic space group P21/c with the cell parameters a = 11.963(12) Å, b = 7.525(10) Å, c = 11.389(14) Å, β = 109.88(4)°, and Z = 4. Compound II crystallizes in the monoclinic space group P21/n with a = 9.066(6) Å, b = 6.793(3) Å, c = 20.112(7) Å, β = 97.54(3)°, and Z = 4. Compound III crystallizes in the monoclinic space group P21/c with a = 9.141(2) Å, b = 17.056(4) Å, c = 9.470(2) Å, β = 90.29(2)°, and Z = 4. Compound IV crystallizes in the orthorhombic space group Ibam with a = 18.202(2) Å, b = 8.7596(7) Å, c = 9.7699(8) Å, and Z = 4. Compound V crystallizes in the orthorhombic space group Ccca with a = 17.529(9) Å, b = 36.43(3) Å, c = 9.782(4) Å, and Z = 8. Compound VI crystallizes in the orthorhombic space group Ibam with a = 18.29(5) Å, b = 8.81(2) Å, c = 9.741(10) Å, and Z = 4. Compound VII crystallizes in the orthorhombic space group Pnma with a = 16.782(2) Å, b = 6.6141(6) Å, c = 6.5142(6) Å, and Z = 4. The sulfur compounds are in most cases isostructural to their selenium counterparts. By controlling experimental conditions, these structures can be placed in quasi-quaternary phase diagrams, which show the reaction conditions necessary to obtain a particular thiophosphate anionic unit in the crystalline product. These structures have been characterized by Raman and IR spectroscopy and UV−vis diffuse reflectance optical band gap analysis.
