Ag5U(PS4)3: A Transition-Metal Actinide Phosphochalcogenide

Mesbah, Adel; Prakash, Jai; Lebègue, Sébastien; Beard, Jessica C.; Malliakas, Christos D.; Ibers, James A.

doi:10.1021/acs.inorgchem.8b02739

Cited by 3 publications

(3 citation statements)

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“…Oxyphosphate ligands have been studied extensively and are known to exhibit various oxidation states, rich structural diversity, and different structural units ranging from isolated P(V)O 4 3– groups to infinite (P(V)O 3 – ) ∞ chains. − In contrast, there are only a few thiophosphate ligands reported so far, i.e., thiophosphate, P(V)S 4 3– , − thiopyrophosphate, P(V) 2 S 7 4– , ,, hexathiometadiphosphate, P(V) 2 S 6 2– , − and hexathiohypophosphate, P(IV) 2 S 6 4– . ,− The latter, P(IV) 2 S 6 4– , contains phosphorus in the +4 oxidation state and demonstrates a unique stability in aqueous solutions. The former three are highly moisture-sensitive, but can be stabilized in the crystal lattice for extended periods of time. , The majority of known thiophosphates are composed of either the simplest thiosphosphate unit, P(V)S 4 3– , or hexathiohypophosphite, P(IV) 2 S 6 4– anions.…”

Section: Introductionmentioning

confidence: 99%

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

et al. 2019

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To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP 2 S 6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP 2 S 7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie−Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP 2 S 7 sample. UV−vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.

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Section: Introductionmentioning

confidence: 99%

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

et al. 2019

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“…Thus, the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence 72 In the way of generalizations there is no direct influence of the dimensionality of the structure or An oxidation state on the value of the band gap. However, the nature of the actinide is important as Th 4+ compounds have larger band gaps than their U 4+ analogues.…”

Section: Physical and Electronic Propertiesmentioning

confidence: 99%

Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements

2016

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This review focuses on the results of exploratory syntheses of alkaline-earth-metal actinide chalcogenides Ak-An-Q (Ak = Ba, Sr; An = Th, U; Q = S, Se, and Te). About thirty new compounds are described. Although the basic building blocks of their structures are usually AnQ octahedra and AkQ bicapped trigonal prisms, these are combined in diverse ways to afford eleven new structure types. The structures reconfirm the prevailing presence of An in chalcogenides, although some of the compounds discovered are mixed An/An systems, and a few contain only An. The tendency of the chalcogens to form Q-Q bonds is again evident from the presence of S-S single bonds and infinite Te-Te-Te linear chains. The latter possess interatomic distances of lengths greater than that of a Te-Te single bond but less than that of a Te-Te van der Waals interaction. Assignment of formal oxidation states in compounds containing these chains is arbitrary at best. Addition of metal atoms (M) affords quaternary structures, some of which show remarkable flexibility in the positions of the An and M atoms, and in such compounds the nature of the M elements influences directly the dimensionality of the resultant structure. The presence of adventitious oxygen, often from etching of the fused-silica tubes by oxyphilic An elements, results in new quintary compounds that show remarkable structural variations with change of M. The compounds discussed have shown transport and electronic structures that range from metallic-like to semiconducting. We find, with the exception of BaUSe, when comparisons can be made that the values of the calculated band gaps are reasonably close but usually lower than the experimentally derived values. Thus the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence of suitable crystals, and hence experimental measurements, it still may be possible to offer credible predictions of some of the magnetic and electronic properties of the compounds.

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“…Numerous uranium chalcogenide compounds exhibiting complex structures, promising magnetic and electronic properties, and rare oxidation states − have been obtained from sulfide, halide, and other fluxes. − Driven by interest in the magnetic properties of uranium(IV) compounds that offer a convenient probe for the magnetic behavior of 5f electrons, we have applied the iodide flux crystal growth approach to uranium(IV) thiophosphates and obtained a new family of compounds with complex topologies . Extending this approach to new families of uranium compounds, we performed several syntheses involving silicon sulfide in an attempt to increase the content of positively charged countercations and extend the uranium thioanion framework by replacing PS 4 3– anions with SiS 4 4– .…”

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confidence: 99%

Targeted Synthesis of Uranium(IV) Thiosilicates

2019

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Two new uranium(IV) thiosilicates, Cs2Na4[U2(SiS4)2(Si2S8)] and Cs2.12Na3.88[U2(SiS4)2(Si2S7)], were obtained by flux crystal growth using SiS2 as a silicon source. The former compound contains a novel Si2S8 6– unit that features a terminal persulfide group. The magnetic susceptibility measurements performed on this compound revealed paramagnetic behavior with a moment of 3.49 μB per uranium atom as obtained from a Curie–Weiss law fit and showed no magnetic transition down to 2 K. The structures are based on closely related isomeric planar and 3D topologies that can be transformed into one another by a rotation of the structural units.

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Ag₅U(PS₄)₃: A Transition-Metal Actinide Phosphochalcogenide

Cited by 3 publications

References 56 publications

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements

Targeted Synthesis of Uranium(IV) Thiosilicates

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