Targeted synthesis of uranium(IV) thiosilicates

Article abstract of DOI:10.1021/acs.inorgchem.9b01307

Two new uranium(IV) thiosilicates, Cs₂Na₄[U₂(SiS₄)₂(Si₂S₈)] and Cs_2.12Na_3.88[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 μ_B 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.

Full text of DOI:10.1021/acs.inorgchem.9b01307

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Targeted Synthesis of Uranium(IV) Thiosilicates
Vladislav V. Klepov, Mark D. Smith, and Hans-Conrad zur Loye*
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
S Supporting Information
*
In this Communication, we report on the synthesis,
ABSTRACT: Two new uranium(IV) thiosilicates,
C s 2 N a 4 [ U 2 ( S i S 4 ) 2 ( S i 2 S 8 ) ] a n d
Cs2.12Na3.88[U (SiS ) (Si S )], were obtained by flux
structures, and properties of Cs Na [U (SiS ) (Si S )] (1)
2
4
2
4 2
2 8
and Cs2.12Na3.88[U (SiS ) (Si S )] (2), the first uranium(IV)
2
4 2
2 7
2
4
2
2 7
thiosilicates obtained in a controlled reaction. Both com-
pounds were crystallized from an iodide flux employing
uranium(IV), silicon(IV), and sodium sulfides as starting
reagents. The two novel crystal structures exhibit similar edge-
sharing uranium chains that are connected by thiopyrosilicate
crystal growth using SiS as a silicon source. The former
2
6
−
compound contains a novel Si2S8 unit that features a
terminal persulfide group. The magnetic susceptibility
measurements performed on this compound revealed
6−
6−
paramagnetic behavior with a moment of 3.49 μ per
Si2S7 and unprecedented Si2S8 units (Figure 1) into sheets
B
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.
espite recent advances in the development of structure
D
and property prediction methodologies, exploratory
synthesis of new materials still plays a pivotal role in modern
chemistry and materials science. Based mainly on the trial-and-
error approach, it can be greatly enhanced by incorporating
existing chemical knowledge, such as chemical trends deduced
from related chemical systems, and syntheses and, thereby,
results in a more effective, targeted synthesis route. One such
synthetic route that often results in single crystals is flux crystal
growth. This method allows for short reaction times, access to
thermodynamic and kinetic products, high-quality crystals,
high yields, and phase purity; as a bonus, by benefiting from
prior knowledge, it significantly improves the efficiency of
exploratory syntheses, successfully paving the way to new
materials and greatly facilitating the investigation of their
Figure 1. Disordered Si2S86 and Si2S76− units in the structures of 1
(left) and 2 (right). Sulfur and silicon atoms are yellow and gray,
respectively.
−
or a framework. Magnetic susceptibility measurements revealed
paramagnetic behavior of 1, and its UV−vis spectrum is similar
to that of uranium(IV) thiophosphate compounds.
Both compounds were obtained via the flux crystal growth
25
method using alkali iodide fluxes. For both reactions, the
choice of the starting materials was made based on the need to
achieve reduced reaction times and to ensure that the desired
oxidation states of the components would be maintained. We
obtained both silicon and uranium sulfides by a direct reaction
between the elements (see the Supporting Information for a
1
−5
physical properties.
detailed description). The starting materials, US , SiS , and
Numerous uranium chalcogenide compounds exhibiting
complex structures, promising magnetic and electronic proper-
2
2
Na S, were then reacted in evacuated flame-sealed silica tubes
2
6
−11
containing the cesium iodide (CsI) fluxes. 2 was obtained from
a CsI/sodium iodide (NaI) eutectic flux (48.6 mol % NaI; mp
ties, and rare oxidation states
sulfide, halide, and other fluxes.
have been obtained from
Driven by interest in the
12−22
4
20 °C) as an intimate mixture of the thiosilicate product and
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
the UOS byproduct, the presence of which prevented the
property measurements of 2. A sample of 1 contaminated with
a minor US impurity was isolated from a pure CsI flux. The
3
2
3
thiosilicate products were found to be air-sensitive and
decomposed in humid air in less than 12 h.
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
To probe the influence of the SiS starting material on the
2
reaction outcome and to check the reproducibility of the
syntheses, we performed additional reactions using a CsI/NaI
eutectic flux along with a control reaction using the same molar
ratio of elemental silicon and sulfur. The initial reaction was
3−
4−
by replacing PS4 anions with SiS4 . It is worth noting that
no uranium thiosilicates were known until 2015 when Mesbah
et al. serendipitously obtained Ba Si US and Ba SiFeUS ,
8
2
14
8
14
where the silica tubes that contained the reaction served as the
silicon source.
Received: May 3, 2019
2
4
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b01307
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
28
found to be reproducible with the use of SiS as a silicon
source, whereas the reaction involving elemental silicon and
sulfur did not result in 2 according to powder X-ray diffraction
bond distances in other reported compounds. The Si2S86−
unit is disordered over two positions by an inversion center
and edge-shares with two uranium atoms on one end and two
on the other, using all of its six terminal sulfur atoms for
bonding.
2
(
PXRD; Figure S2). This suggests that not only is the presence
of the proper amount of silicon and sulfur necessary for
obtaining the desired uranium thiosilicates but also the
chemical forms of the silicon and sulfur play a critical role in
influencing the reaction pathway leading to product formation,
indicative of a kinetic route to the resulting product.
Despite the rich structural chemistry of silicon oxide
materials, which exhibit numerous structural units, ranging
from the simple orthosilicate SiO4 through complex chain
4−
and layered motifs to 3D SiO , the library of known thiosilicate
2
Single crystals of both compounds were analyzed using X-ray
units is much more sparse and consists of only three examples.
2
6
4−
29−33
diffraction. They were found to crystallize in the monoclinic
crystal system, space groups C2/m and C2/c for 1 and 2,
Among them, the most common one is the SiS anion,
4
6−
4− 27,34−37
while the other two, Si S and Si2S6
,
are much less
2
7
4
+
6−
respectively. 1 exhibits a layered structure composed of U
common. The Si2S8 unit, reported herein for the first time,
represents a new addition to the library of thiosilicate units.
While the tendency of chalcogenides to form polychalcogenide
cations connected through SiS44 and Si2S8 anions (Figure
−
6−
2
). The interlayer space is occupied by the alkali cations Cs+
2−
38−40
Qn (Q = S, Se, Te) units is well-known,
the data on
such units in chalcoanions are rather limited. For example,
perselenido bridges have been observed in A Ge Se (A = Rb,
4
4
12
41
42
Cs). These and other compounds, such as Cs P S ,
2
4 10
exemplify the marked difference between the chalco- and
oxoanion chemistry because peroxo groups are rarely present
in oxides.
Compound 2 crystallizes in a framework structure that
consists of uranium atoms connected by thiosilicate SiS and
4
thiopyrosilicate Si S units. US square antiprisms share edges
2
7
8
to form chains, and the bridging thiosilicate units connect
them into a 3D framework (Figure 2d). The bond lengths and
angles within the US coordination polyhedra and thiosilicate
8
units fall within the expected ranges. The thiopyrosilicate units
are severely disordered, most likely because of free rotation of
the bridging sulfur atom within the unit. The disorder was
resolved by introducing many partially occupied sulfur sites
and splitting each silicon position into two. Both room- and
low-temperature (100 K) data sets resulted in similar models,
suggesting that the disorder is either of a static nature or
requires even lower temperature to achieve an energy
minimum with fully occupied positions.
A comparison of the structures reveals a structure formation
trend that is similar to that observed in the uranium
23
thiophosphate compounds. The uranium polyhedra function
as tetracoordinate nodes in both compounds, whereas the SiS4
tetrahedra play the roles of bridging units. In both structures,
US polyhedra edge-share to form chains that are connected to
8
Figure 2. Thiopyrosilicate units in the structures of 1 and 2 (a and b)
and connections of US8 coordination polyhedra in sheets and a
framework (c and d), respectively, with their schematic representa-
each other through the thiopyrosilicate units. As schematically
shown in Figure 2e, in the layered structure of 1, the chains are
parallel to each other. The layers in 1 can be transformed to
the 3D framework of 2 by rotating half of the chains, as is
shown in Figure 2f, and creating new bonds with the chains
from the successive layers.
tions (e and f). Thiosilicate units SiS are omitted for clarity. Sulfur
4
atoms and silicon and uranium polyhedra are yellow, gray, and green,
respectively.
+
and Na . The uranium atoms form coordination polyhedra in
Magnetic susceptibility measurements were performed on 1
and revealed Curie−Weiss behavior in the region of 50−300 K
the shape of a distorted tetragonal antiprism with U−S bond
lengths ranging from 2.7467(5) to 2.9160(4) Å. Each US
(Figure 3). An effective magnetic moment of 3.49 μ per
B
8
polyhedron shares two edges with other uranium atoms,
uranium atom was calculated from a Curie−Weiss fit of the
forming a US S chain along the b axis. In 1, the thiosilicate
inverse susceptibility data. Given the presence of a minor US
4
4/2
3
4
−
unit SiS4 adopts a tetrahedral geometry with S−Si−S angles
within the range of 106.04(3)−112.15(3)° and Si−S distances
of 2.0307(18)−2.1353(10) Å, in good agreement with
impurity detected from PXRD, which slightly increases the
observed moment of the sample because of the lower molar
mass of the impurity, the effective magnetic moment of the
uranium atoms in the sample is slightly lower than the value of
2
4
literature values. To the best of our knowledge, the other
thiosilicate unit, Si2S86 , has never previously been observed. It
consists of two vertex-sharing thiosilicate tetrahedra, as in the
−
3
3.58 μ calculated for a H ground state. Despite the presence
B
4
of infinite edge-sharing uranium(IV) chains in the structure,
there is no magnetic transition observed down to 2 K,
indicating that the adjacent uranium atoms do not substantially
couple magnetically.
thiopyrosilicate unit Si2S76
−
,
27
with one terminal sulfur atom
replaced by a persulfide S22 group (Figure 2a). The S−S bond
length is 2.1564(16) Å, which is consistent with persulfide
−
B
DOI: 10.1021/acs.inorgchem.9b01307
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Research is supported by the Division of Materials Sciences
and Engineering, U.S. Department of Energy, Office of Basic
Energy Sciences, under Award DE-SC0018739.
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DOI: 10.1021/acs.inorgchem.9b01307
Inorg. Chem. XXXX, XXX, XXX−XXX