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

Vladislav V Klepov; Hans-Conrad Zur Loye

doi:10.1021/acs.inorgchem.8b01733

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

Inorg Chem. 2018 Sep 4;57(17):11175-11183. doi: 10.1021/acs.inorgchem.8b01733. Epub 2018 Aug 16.

Authors

Vladislav V Klepov¹, Hans-Conrad Zur Loye¹

Affiliation

¹ Department of Chemistry and Biochemistry , University of South Carolina , 631 Sumter Street , Columbia , 29208 South Carolina , United States.

PMID: 30113829
DOI: 10.1021/acs.inorgchem.8b01733

Abstract

Six new uranium thiophosphates, Cs₅Na₆[U(PS₄)₄](PS₄) (1), Rb₅Na₃[U(PS₄)₄] (2), CsNa[U(PS₄)₂] (3), Cs_1.67Na_0.52I_0.19[U(PS₄)₂] (4), Cs_1.033Na_1.343I_0.376[U(PS₄)₂] (5), and Rb_1.35Na_0.93I_0.28[U(PS₄)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 PS₄ group coordination modes can result in an isolated [U(PS₄)₄]^8- unit, a [U(PS₄)₂]^2- chain, or a [U(PS₄)₂]^2- slab. Optical and magnetic properties of 3 and 4 were collected. Both compounds exhibit paramagnetic behavior, and CsNa[U(PS₄)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.