beta-Bi(4)(P(2)Se(6))(3): A New Ternary Selenophosphate Obtained in a P(2)Se(5) Flux.

Bi metal dissolves in excess molten phosphorus selenide at 500 degrees C to yield black, rodlike, air- and water-stable beta-Bi(4)(P(2)Se(6))(3) crystals. The phase crystallizes in the triclinic space group P&onemacr; (No. 2) with the room-temperature cell parameters a = 12.

Palladium Chemistry in Molten Alkali Metal Polychalcophosphate Fluxes. Synthesis and Characterization of K(4)Pd(PS(4))(2), Cs(4)Pd(PSe(4))(2), Cs(10)Pd(PSe(4))(4), KPdPS(4), K(2)PdP(2)S(6), and Cs(2)PdP(2)Se(6).

The reaction of Pd with a molten mixture of A(2)Q(x)()/P(2)Q(5)/Q (A = K, Q = S, x = 3; A = Cs, Q = Se, x = 1) produced the molecular compounds K(4)Pd(PS(4))(2) (I), Cs(4)Pd(PSe(4))(2) (II), and Cs(10)Pd(PSe(4))(4) (III) and the solid-state KPdPS(4) (IV), K(2)PdP(2)S(6) (V), and Cs(2)PdP(2)Se(6) (VI). Compounds I-III are air and water sensitive, while IV-VI are air and water stable. All crystals are red or dark red except those of VI, which are black.

Complex Fluids Based on the Flexible One-Dimensional Mineral Polymers [K(MPS )] (M=Ni, Pd): Autofragmentation to Concave, Cyclic (PPh ) [(NiPS ) ].

A remarkable autofragmentation/rearrangement sequence results in the unprecedented formation of inorganic concave cyclic anion [(NiPS ) ] (structure shown on the right) upon dissolving the potassium salt of the charged mineral polymer [NiPS ] in DMF; the initial complex fluid has a transient anisotropic texture that can be identified by optical microscopy under polarized light. In contrast, the complex fluid that results upon dissolving [PdPS ] is stable up to 323 K as persistent, flexible, charged chains.