Complex Topologies from Simple Building Blocks: Uranium(IV) Thiophosphates

Six new uranium thiophosphates, Cs 5 Na 6 [U(PS 4 ) 4 ](PS 4 ) (1), Rb 5 Na 3 [U(PS 4 ) 4 ] (2), CsNa[U(PS 4 ) 2 ] (3), Cs 1.67 Na 0.52 I 0.19 [U(PS 4 ) 2 ] (4), Cs 1.033 Na 1.343 I 0.376 [U(PS 4 ) 2 ] (5), and Rb 1.35 Na 0.93 I 0.28 [U(PS 4 ) 2 ] (6), were obtained from halide flux reactions and characterized using single-crystal X-ray diffraction. The structures of these compounds consist of a pseudotetrahedral uranium unit that in combination with a set of PS 4 group coordination modes can result in an isolated [U(PS 4 ) 4 ] 8- unit, a [U(PS 4 ) 2 ] 2- chain, or a [U(PS 4 ) 2 ] 2- slab. Optical and magnetic properties of 3 and 4 were collected. Both compounds exhibit paramagnetic behavior, and CsNa[U(PS 4 ) 2 ] (3) exhibits a magnetic transition at 200-225 K between two paramagnetic states that both have similar effective magnetic moments of 4.13 and 4.19 μ B /formula unit, and strong antiferromagnetic interactions with θ = -183 and -172 K, for the high- and low-temperature states, respectively.