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Article

A Challenge toward Novel Quaternary Sulfides SrLnCuS3 (Ln = La, Nd, Tm): Unraveling Synthetic Pathways, Structures and Properties

by
Anna V. Ruseikina
1,
Maxim V. Grigoriev
1,
Leonid A. Solovyov
2,
Vladimir A. Chernyshev
3,
Aleksandr S. Aleksandrovsky
4,5,
Alexander S. Krylov
4,
Svetlana N. Krylova
4,
Nikolai P. Shestakov
4,
Dmitriy A. Velikanov
4,
Alexander A. Garmonov
6,
Alexey V. Matigorov
1,
Marcel A. Eberle
7,
Thomas Schleid
7 and
Damir A. Safin
8,9,10,*
1
Laboratory of Theory and Optimization of Chemical and Technological Processes, University of Tyumen, 625003 Tyumen, Russia
2
Federal Research Center KSC SB RAS, Institute of Chemistry and Chemical Technology, 660036 Krasnoyarsk, Russia
3
Institute of Natural Sciences and Mathematics, Ural Federal University named after the First President of Russia B.N. Yeltsin, Mira Str. 19, 620002 Ekaterinburg, Russia
4
Kirensky Institute of Physics, Federal Research Center KSC SB RAS, 660036 Krasnoyarsk, Russia
5
Department of Photonics and Laser Technology, Siberian Federal University, 660079 Krasnoyarsk, Russia
6
Institute of Physics and Technology, University of Tyumen, Volodarskogo Str. 6, 625003 Tyumen, Russia
7
Institute of Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, Germany
8
Scientific and Educational and Innovation Center for Chemical and Pharmaceutical Technologies, Ural Federal University named after the First President of Russia B.N. Yeltsin, Mira Str. 19, 620002 Ekaterinburg, Russia
9
«Advanced Materials for Industry and Biomedicine» Laboratory, Kurgan State University, Sovetskaya Str. 63/4, 640020 Kurgan, Russia
10
University of Tyumen, Volodarskogo Str. 6, 625003 Tyumen, Russia
*
Author to whom correspondence should be addressed.
Int. J. Mol. Sci. 2022, 23(20), 12438; https://doi.org/10.3390/ijms232012438
Submission received: 27 September 2022 / Revised: 7 October 2022 / Accepted: 10 October 2022 / Published: 18 October 2022
(This article belongs to the Collection Feature Papers in Materials Science)
Browse Figures
Versions Notes

Abstract

:
We report on the novel heterometallic quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm), obtained as both single crystals and powdered samples. The structures of both the single crystal and powdered samples of SrLaCuS3 and SrNdCuS3 belong to the orthorhombic space group Pnma but are of different structural types, while both samples of SrTmCuS3 crystallize in the orthorhombic space group Cmcm with the structural type KZrCuS3. Three-dimensional crystal structures of SrLaCuS3 and SrNdCuS3 are formed from the (Sr/Ln)S7 capped trigonal prisms and CuS4 tetrahedra. In SrLaCuS3, alternating 2D layers are stacked, while the main backbone of the structure of SrNdCuS3 is a polymeric 3D framework [(Sr/Ln)S7]n, strengthened by 1D polymeric chains (CuS4)n with 1D channels, filled by the other Sr2+/Ln3+ cations, which, in turn, form 1D dimeric ribbons. A 3D crystal structure of SrTmCuS3 is constructed from the SrS6 trigonal prisms, TmS6 octahedra and CuS4 tetrahedra. The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS6)n and 1D free channels. In both crystal structures of SrLaCuS3 obtained in this work, the crystallographic positions of strontium and lanthanum were partially mixed, while only in the structure of SrNdCuS3, solved from the powder X-ray diffraction data, were the crystallographic positions of strontium and neodymium partially mixed. Band gaps of SrLnCuS3 (Ln = La, Nd, Tm) were found to be 1.86, 1.94 and 2.57 eV, respectively. Both SrNdCuS3 and SrTmCuS3 were found to be paramagnetic at 20–300 K, with the experimental magnetic characteristics being in good agreement with the corresponding calculated parameters.

1. Introduction

Layered chalcogenides containing d-metals are of particular interest due to their valuable properties, as well as being used as superconductors [1], magnetic [2,3] and thermoelectric materials [4], materials for infrared and nonlinear optics [5,6,7] and catalysts [8]. The quaternary chalcogenides ABCX3 (A is an alkali or alkaline earth metal, Eu; B is a d- or f-element; C is a d-element; X is a chalcogenide) produce layered and/or channel structures, crystallizing in various structural types [9,10,11,12,13,14,15,16,17,18,19,20,21,22,23]. An overwhelming majority of the crystal structures of ABCX3 exhibit 2D anionic layers [BCX3]n− with trapped An+ cations. Both the nature and charge of An+ affect the lattice distortion, electronic structure, phonon dispersion, electrical properties, and heat transfer properties in the crystal structure [24]. ABCX3 compounds exhibit very low lattice thermal conductivity [25,26,27], promising thermoelectric characteristics [24,28] and high photovoltaic efficiency [27]. Thus, thermodynamically stable quaternary compounds are potential high-performance thermoelectrics, thermal barrier coatings, and thermal data-storage devices [26,29,30,31,32]. Furthermore, semiconductor, magnetic, optical, and thermodynamic properties have also been described for these compounds [4,9,10,11,12,13,14,15,16,17,18,19,20,23,24,33,34,35,36,37,38].
Of the ABCX3 compounds, the quaternary chalcogenides ALnCuX3 are of particular interest, since transition and rare earth elements exhibit rich crystal chemistry and specific spectroscopic properties. According to quantum mechanical calculations, the band gap of SrLnCuS3 is 1.00–1.51 eV [26], indicating that these compounds are promising materials for solar cells with an efficiency of about 20% [39,40,41,42]. However, the lack of experimental data on the band gap of SrLnCuS3 limits their practical utilization.
Polycrystalline samples of SrLnCuS3 were obtained by the melting of a stoichiometric ratio of sulfides SrS, Ln2S3 and Cu2S, followed by annealing at 970–1170 K for 2–3 (!) months [22,34,35,36,43,44,45]. Single-crystal samples were synthesized from elemental Sr, Cu and Ln (Ln = Nd, Y, Sc) using a halide flux at 1070 K for 8 days [46,47]. Recently, we have reported on the synthesis of EuLnCuS3 by the sulfidation of a mixture of oxides obtained by thermolysis of co-crystallized copper nitrate and rare-earth nitrates for 25 h [48]. Thus, using this approach would, likely, significantly reduce the synthesis time towards SrLnCuS3. Notably, strontium oxide is more active than europium oxide with respect to the material of the reactor used for synthesis due to the presence of an alkaline earth element. Therefore, it is suggested that the initial synthesis temperatures to produce SrLnCuS3 should be lower than those of EuLnCuS3.
In the literature, the crystal structures of some SrLnCuS3 have already been reported [21,22,34,35,36,43,44,45,46,47]. For SrLnCuS3, two types of orthorhombic crystal structures with Pnma symmetry and one type with Cmcm symmetry were revealed [22]. Sulfides SrLnCuS3 (Ln = La–Nd) crystallize in the BaLaCuS3 structural type, and the crystallographic positions of the Sr2+ and Ln3+ ions are partially mixed by 21% in SrLaCuS3 [22,43], by 16% in SrCeCuS3 [44] and by 11% in SrPrCuS3 [22,43], while in SrNdCuS3 the Sr2+ and Ln3+ cations occupy two different crystallographic positions [46]. It should also be noted that, for SrNdCuS3, the second modification of the structural type Eu2CuS3 was obtained [46], while for SrCeCuS3, a high-temperature polymorphic modification of the structural type Ba2MnS3 with a partially mixed crystallographic positions of the Sr2+ and Ce3+ ions was also revealed [44].
The isostructural quaternary sulfides EuLnCuS3 [37,49] and selenides EuLnCuSe3 [23] and SrLnCuSe3 [50,51] always start to crystallize in the structural type Ba2MnS3. Due to the similar ionic radii of Eu2+ and Sr2+ (1.17 and 1.18 Å, respectively [52]), the structural types of EuLnCuS3 and SrLnCuS3 should also be similar. Thus, it can tentatively be assumed that SrLaCuS3 will also crystallize in the structural type Ba2MnS3. Sulfides SrLnCuS3 (Ln = Sm [22], Gd [22], Ho [35], Y [47]) belong to the structural type Eu2CuS3, while SrLnCuS3 (Ln = Er [45], Yb [45], Lu [22], Sc [36]) are of the structural type KZrCuS3. In all the listed compounds, the Eu2+ and Ln3+ ions occupy two crystallographically independent positions. The change of space group from Pnma to Cmcm occurs between SrYCuS3 and SrErCuS3 [23]. SrLnCuS3 melt incongruently at 1429–1712 K [34,43]. SrLaCuS3 and SrPrCuS3 are optically transparent in the IR range from 1800 to 3600 cm−1 [43]. To the best of our knowledge, other physical properties of sulfides SrLnCuS3 have not been reported so far.
With all this in mind, in this work we have focused on the synthesis of SrLnCuS3 (Ln = La, Nd, Tm), as well as studying their crystal structures, magnetic and optical properties.

2. Results and Discussion

The heterometallic quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm) were obtained both in the form of single crystals as well as powdered samples. The former synthetic procedure requires heating a stoichiometric ratio of the elements Sr, Cu, Ln and S in the presence of CsBr as a flux for 8 days at 1070 K, while the latter synthetic approach significantly decreases the reaction time in comparison to both a single-crystal method and the sulfide-melting method [22,35,43,44,45,47].
To date, for the quaternary sulfides, only four crystal structures of SrLnCuS3 (Ln = Nd, Y, Sc), solved from the single-crystal X-ray diffraction data, have been known so far (Table 1) [46,47], while twelve crystal structures of a series of SrLnCuS3 (Ln = La, Ce, Pr, Nd, Sm, Gd, Ho, Er, Tm, Yb, Lu, Sc), solved from the powder X-ray diffraction data, have been reported (Table 2) [22,36,44,45].
In the present work, we report for the first time the crystal structures of SrLaCuS3 and SrTmCuS3 (Table 1), solved from the single-crystal X-ray diffraction data, as well as the crystal structure of SrLnCuS3 (Ln = La, Nd, Tm), solved from the powder X-ray diffraction data (Table 2). Notably, the same synthetic approach for the formation of single crystals yields one structural type, Ba2MnS3, for SrLaCuS3, and two structural types, BaLaCuS3 and Eu2CuS3, for SrNdCuS3 of the orthorhombic space group Pnma, while for SrTmCuS3, the structural type KZrCuS3 of the orthorhombic space group Cmcm was established (Table 1). However, different synthetic approaches toward powdered samples yield two structural types, BaLaCuS3 and Ba2MnS3, for SrLaCuS3, one structural type, BaLaCuS3, for SrNdCuS3 of the same orthorhombic space group Pnma, and one structural type, KZrCuS3, of the orthorhombic space group Cmcm for SrTmCuS3 (Table 2). Interestingly, while the b axis in the structures of SrLaCuS3 and SrNdCuS3 is very similar and varies from 4.0072(3) Å to 4.11053(6) Å, the a and c axes differ significantly ranging from 8.1682(6) Å to 16.0394(11) Å (Table 1 and Table 2). Furthermore, the cell volume is almost the same in the structures of SrLaCuS3, regardless of the structural type, and of 533.85(7)–535.97(1) Å3, but differs in the structures of SrNdCuS3. Particularly, the cell volume is 518.63(2)–519.14(1) Å3 in the structural type BaLaCuS3, and is remarkably larger in the structural type Eu2CuS3 (545.96(3) Å3). The cell volume in the structures of SrLaCuS3 is smaller and of 510.50(6)–511.34(3) Å3.
It should also be noted that in both crystal structures of SrLaCuS3 obtained in this work, the crystallographic positions of strontium and lanthanum were partially mixed by about 50% and 45%, respectively, while only in the structure of SrNdCuS3, solved from the powder X-ray diffraction data, the crystallographic positions of strontium and neodymium were partially mixed by about 11% (Table 3). In both structures of SrTmCuS3, each atom fully occupies its own crystallographical position (Table 3).
A 3D crystal structure of both SrLaCuS3 and SrNdCuS3 was constructed from the (Sr1/Ln1)S7- and (Sr2/Ln2)S7-capped trigonal prisms as well as CuS4 tetrahedra (Figure 1). However, different structural types of these compounds are clearly reflected in the packing of coordination polyhedra. Particularly, in the structure of SrLaCuS3, the (Sr1/La1)S7-and (Sr2/La2)S7-capped trigonal prisms each form alternating 2D layers, of which the (Sr1/La1)S7-based layers are further strengthened by 1D polymeric chains (CuS4)n (Figure 1). The main backbone of the structure of SrNdCuS3 is a polymeric 3D framework [(Sr1/Ln1)S7]n, further strengthened by 1D polymeric chains (CuS4)n, with 1D channels along the b axis, filled by the Sr22+/Ln23+ cations, which, in turn, form 1D dimeric ribbons along the b axis (Figure 1). A 3D crystal structure of SrTmCuS3 differs significantly from the La- and Nd-based derivatives and is constructed from the SrS6 trigonal prisms and TmS6 octahedra as well as CuS4 tetrahedra (Figure 1). The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS6)n and 1D free channels along the a axis (Figure 1).
In the discussed structures of SrLaCuS3, the Sr/La–S bond lengths are 2.910(1)–3.09999(17) Å, while the Sr/Nd–S bonds in the structures of SrNdCuS3 vary in a broader range from 2.843(1) Å to 3.136(2) Å (Table 4). The Sr–S bond lengths in the structures of SrTmCuS3 are similar to those in the La- and Nd-based derivatives, and of 2.966(3)–3.093(2) Å, while the Tm–S bonds are shorter and of 2.703(2)–2.719(2) Å (Table 4). The Cu–S distances within the coordination tetrahedron in all the reported structures vary from 2.325(2) Å to 2.388(3) Å (Table 4).
The IR and Raman spectra of SrLnCuS3 (Ln = La, Nd, Tm) each contain bands exclusively up to about 350 cm−1 (Figure 2), thus the discussed compounds are both IR and Raman transparent, at least in the region of 350–4000 cm−1. The most intense bands in the IR and Raman spectra were observed at about 220–230 and 65–80 cm−1, respectively.
For SrLnCuS3 (Ln = La, Nd, Tm), the experimental band gaps were obtained from the Kubelka–Munk function, and are of 1.86, 1.94 and 2.57 eV, respectively (Figure 3). Notably, the band gap values for SrLaCuS3 and SrNdCuS3 are similar, which might tentatively be explained by the same orthorhombic space group Pnma in the crystal structures of these sulfides, while the crystal structure of the discussed SrTmCuS3 exhibits the orthorhombic space group Cmcm.
The field-dependent magnetic moment of both SrNdCuS3 and SrTmCuS3 at 296 K is linear, which is characteristic for a paramagnetic compound (Figure 4). From this dependence, the effective magnetic moment was calculated as 3.611 and 7.378 μB for the Nd- and Tm-based sulfides, respectively (Table 5). The temperature-dependent reciprocal magnetic susceptibility at 20–300 K is well described by the Curie–Weiss law and is the same in both the zero-field cooled (ZFC) and nonzero-field cooled (FC) modes (Figure 4). As such, the C, μ and θ values were calculated for both compounds at 20–300 K (Table 5). Experimental magnetic characteristics for SrNdCuS3 and SrTmCuS3 are in good agreement with the corresponding calculated parameters, obtained in the model of free ions Nd3+ and Tm3+, respectively (Table 5).

3. Materials and Methods

3.1. Materials

Sr (99.2%), La (99.9%), Tm (99.9%) and CsBr (99.9%) were purchased from ChemPur (Karlsruhe, Germany). Ln2O3 (Ln = La, Nd, Tm; 99.95%) were purchased from the Uralredmet manufacture (Verkhnyaya Pyshma, Russia). Cu (99.9%) was obtained from SZB Tsvetmet, OJSC (Saint Petersburg, Russia), while Cu (99.8%) was purchased from Merck (Darmstadt, Germany). S (99.5%) was purchased from Alfa Aesar (Karlsruhe, Germany). Argon (99.998%) was purchased from Kislorod-Servis (Yekaterinburg, Russia). Concentrated nitric acid (extra-pure grade, 18-4 all-Union State Standard 11125-84) was purchased from Chemreaktivsnab, CJSC (Ufa, Russia). NH4SCN (98%) was obtained from Vekton Ltd. (Saint Petersburg, Russia). SrCO3 (99.8%) was purchased from VitaReaktiv LLC (VitaHim Group, Dzerzhinsk, Russia).

3.2. Methods

The single-crystal X-ray diffraction data for SrLaCuS3 and SrTmCuS3 were collected at room temperature with a Bruker–Nonius κ-CCD diffractometer (Mo-Kα radiation, graphite monochromator) equipped with a CCD detector. The collected intensity data and the numerical correction of the absorption for the measured crystals were processed using the DENZO [54] and HABITUS [55] programs, respectively. The crystal structures were solved and refined using the SHELX-2013 software package [56,57].
The powder X-ray diffraction data for SrLnCuS3 (Ln = La, Nd, Tm; Figure 5) were collected at room temperature with a ДPOH 7 (Burevestnik, Saint Petersburg, Russia) powder diffractometer (Cu-Kα radiation, graphite monochromator). The step size of 2θ was 0.02°, and the counting time was 35 s per step. The lattice parameters were determined using the ITO program [58] and the crystal structures were refined by the derivative difference minimization (DDM) method [59] in the anisotropic approximation for all atoms. The effects of preferred orientation, anisotropic broadening of peak and sample surface roughness and displacement were taken into account during refinement. The data for the isostructural sulfides Ba2MnS3 [60], BaLaCuS3 [61] and KZrCuS3 [9] were used as initial structural models for SrLaCuS3, SrNdCuS3 and SrTmCuS3, respectively. The anomalous disbalance of the thermal parameters of the Sr and Ln sites after the preliminary refinement of the structures indicated a possible mixed filling of their sites due to similar ionic radii. Indeed, refinement of the occupancy of the Sr and Ln sites for the structures of SrLaCuS3 and SrNdCuS3 improved agreement between the calculated and experimental data as well as balanced the thermal parameters.
Scanning electron microscopy (SEM) was performed on a JEOLJSM-6510 LV (JEOL Ltd., Tokyo, Japan) equipped with an energy dispersive spectrometer.
The Fourier-transform infrared (FTIR) absorption spectra in the range of 60–675 cm−1 were recorded on a VERTEX 80v FT-IR spectrometer (Bruker OJSC, Ettlingen, Germany). The attenuated total reflectance infrared (ATR-IR) absorption spectra in the range of 400–4000 cm−1 were recorded on a Cary 630 FTIR spectrometer (Agilent Technologies Inc., Santa Clara, CA, USA) equipped with an ATR attachment and a DTGS detector. The Raman spectra were collected in backscattering geometry using a triple monochromator Horiba JobinYvon T64000 Raman spectrometer (Horiba Ltd., Tokyo, Japan) operating in subtractive mode. The spectral resolution for the recorded Stokes-side Raman spectra was better than 3 cm−1 (this resolution was achieved by using gratings with 1800 grooves mm−1 and 100 µm slits). The single-mode radiation at 532 nm from the Spectra-Physics Excelsior laser was used as an excitation light source, the power on the sample being 5 mW.
The diffuse reflectance spectra were recorded on a UV-2600 spectrophotometer (Shimadzu OJSC, Tokyo, Japan) equipped with an ISR-2600Plus attachment with the photomultiplier PMT of the R-928 type and InGaAs detectors. BaSO4 (99.8%) was used as a standard.
The temperature-dependent (20–300 K) magnetic susceptibilities of SrLnCuS3 (Ln = Nd, Tm) were studied on a Quantum Design MPMS3 SQUID magnetometer in a 200 Oe (15.92 kA m−1) magnetic field. The measurements were performed in the zero-field cooled (ZFC) and nonzero-field cooled (FC) modes. The room temperature magnetic properties of SrLnCuS3 (Ln = Nd, Tm) were studied on a vibrating sample magnetometer with a Puzey electromagnet [62]. The magnetic field was varied in the range –15 ÷ 15 kOe (–1.2 ÷ 1.2 MA m−1).

3.3. Synthesis

Crystalline samples of SrLnCuS3 (Ln = La, Nd, Tm) in the form of single crystals were obtained from a stoichiometric ratio of the elemental strontium, copper, lanthanide and sulfur in the presence of CsBr as a flux. The reaction mixture was heated in an evacuated quartz ampoule for 8 days at 1070 °C. A thin layer of graphite was deposited on the inner wall of the quartz ampoule by a pyrolytic method to avoid side reactions with quartz glass, leading to the formation of oxosilicates. The reaction product was purified from flux residues with demineralized water. The resulting yellow needle-like crystals were suitable for a single-crystal X-ray diffraction analysis.
Powdered samples of SrLnCuS3 (Ln = La, Nd, Tm) were prepared by reductive sulfidation of the oxide mixtures in a flow of H2S and CS2, obtained by decomposition of ammonium thiocyanate (argon was used as a carrier gas) according to a synthetic procedure reported recently [36]. According to X-ray phase analysis, the resulting samples comprised a mixture of oxides Ln2O3, SrLnCuO4, (Sr,Ln)2CuO4, CuSrO2, SrLn2O4, and SrxLn2–xCuO4, which were subjected to reductive sulfidation in a flow of H2S and CS2, yielding the titular quaternary sulfides. Sulfidation was carried out with grinding of the resulting product in three steps: heating at 870 K for 6 h, followed by heating at 1070 K for 4 h, followed by heating at 1170 K for 20 h. This stepwise increasing of the reaction temperature is of importance to avoid the decomposition of reactor material, which, in turn, leads to the formation of silicate impurities. Thus, sulfidation is initiated by isothermal heating at 870 K until the formation of sulfides and oxysulfides, which are not so aggressive with respect to the quartz material. The sulfidation product was cooled in an argon flow. The resulting products SrLnCuS3 were examined by SEM-EDX, and the obtained data are in agreement with the powder X-ray diffraction data and are collected in Table 6.

4. Conclusions

In summary, we report on a novel heterometallic quaternary sulfides SrLnCuS3 (Ln = La, Nd, Tm), which were synthesized both in the form of single crystals as well as powdered samples. The former synthetic procedure allows the production of pure samples but requires heating for 8 days, while the latter synthetic approach significantly decreases the reaction time to less than 2 days. However, synthesis of the powdered samples also yields some impurities, though of minor quantities. The structures of both the single crystal and powdered samples of SrLaCuS3 and SrNdCuS3 belong to the orthorhombic space group Pnma but of different structural types, namely Ba2MnS3, BaLaCuS3 and Eu2CuS3. SrTmCuS3 crystallizes in the orthorhombic space group Cmcm with the structural type KZrCuS3 for both the single crystal and powdered samples.
Three-dimensional crystal structures of the herein-obtained SrLaCuS3 and SrNdCuS3 are formed from the (Sr/Ln)S7-capped trigonal prisms as well as CuS4 tetrahedra, however, yielding different packing of coordination polyhedra. Particularly in SrLaCuS3, alternating 2D layers are stacked, while the main backbone of the structure of SrNdCuS3 is a polymeric 3D framework [(Sr/Ln)S7]n, strengthened by 1D polymeric chains (CuS4)n, with 1D channels, filled by the other Sr2+/Ln3+ cations, which, in turn, form 1D dimeric ribbons. A 3D crystal structure of SrTmCuS3 is constructed from the SrS6 trigonal prisms, TmS6 octahedra and CuS4 tetrahedra. The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS6)n and 1D free channels. Different crystal packings in the reported structures are, most likely, explained by both the formation of different structural types, as well as different Sr- and Ln-based coordination polyhedra. Furthermore, in both crystal structures of SrLaCuS3 obtained in this work, the crystallographic positions of strontium and lanthanum are partially mixed, while only in the structure of SrNdCuS3, solved from the powder X-ray diffraction data, are the crystallographic positions of strontium and neodymium partially mixed.
The optical properties of SrLnCuS3 (Ln = La, Nd, Tm) were revealed by diffuse reflectance spectroscopy, and the band gaps were found to be 1.86, 1.94 and 2.57 eV, respectively. Similar band gap values for SrLaCuS3 and SrNdCuS3 might tentatively be explained by the same orthorhombic space group Pnma.
Finally, SrNdCuS3 and SrTmCuS3 are paramagnetic at 20–300 K. Experimental magnetic characteristics for these sulfides are in good agreement with the corresponding calculated parameters, obtained in the model of free ions Nd3+ and Tm3+, respectively.

Author Contributions

Conceptualization, A.V.R.; software, D.A.S.; validation, D.A.S. and A.V.R.; formal analysis, L.A.S., A.V.R., M.V.G., S.N.K., A.A.G., V.A.C. and M.A.E.; investigation, A.V.R., M.V.G., A.S.K., N.P.S., D.A.V., A.V.M. and M.A.E.; resources, A.V.R. and T.S.; data curation, A.V.R., A.S.A., T.S. and D.A.S.; writing—original draft preparation, A.V.R., A.A.G., A.S.A. and S.N.K.; writing—review and editing, A.V.R., T.S., A.A.G. and D.A.S.; visualization, A.V.R., A.A.G. and D.A.S.; project administration, A.V.R.; funding acquisition, A.V.R., M.V.G. and T.S. All authors have read and agreed to the published version of the manuscript.

Funding

The research was funded by the Tyumen Oblast Government, as part of the West-Siberian Interregional Science and Education Center’s project No. 89-DON (3). This work was supported by state assignment of the Ministry of Science and Higher Education of the Russian Federation (Project Reg. No. 720000Φ.99.1.Б385AA13000).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Acknowledgments

This work was partially performed using resources of the Research Resource Center «Natural Resource Management and Physico-Chemical Research», and the laboratory for electron and probe microscopy of the Scientific and Educational Center (SEC) for Nanotechnologies (University of Tyumen). The use of the equipment of Krasnoyarsk Regional Center of Research Equipment of Federal Research Center «Krasnoyarsk Science Center SB RAS» is acknowledged.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. View of the crystal structures of SrLnCuS3 (Ln = La, top-left; Nd, top-right, Tm, bottom) together with the coordination polyhedra formed by the metal ions. Color code: green polyhedron = (Sr1/La1)S7, (Sr1/Nd1)S7 and SrS6; blue polyhedron = (Sr2/La2)S7, (Sr2/Nd2)S7 and TmS6; burnt orange polyhedron = CuS4. Symmetry codes for SrLaCuS3: (i) x, –1 + y, z; (ii) 1/2 + x, −1/2 − y, 1/2 − z; (iii) 1/2 + x, 1/2 − y, 1/2 − z; (iv) 1/2 − x, −y, −1/2 + z; (v) 1/2 − x, 1 − y, −1/2 + z; (vi) −1/2 + x, 1/2 − y, 1/2 − z; (vii) x, 1 + y, z; (viii) 1 − x, 1/2 + y, −z; (ix) −1/2 + x, 1/2 − y, 1/2 − z. Symmetry codes for SrNdCuS3: (i) x, −1 + y, z; (ii) 1/2 − x, −y, 1/2 + z; (iii) 1/2 − x, −1 − y, 3/2 − z; (iv) −1/2 + x, −1/2 − y, 3/2 − z; (v) 1/2 + x, 1/2 − y, 3/2 − z; (vi) x, 1 + y, z; (vii) 1/2 + x, −1/2 − y, 3/2 − z. Symmetry codes for SrTmCuS3: (i) −x, −y, −z; (ii) −x, −y, −1/2 + z; (iii) 1 + x, y, z; (iv) 1 + x, −y, −z; (v) −1/2 − x, 1/2 + y, 1/2 − z; (vi) −1/2 + x, 1/2 + y, z; (vii) −3/2 − x, 1/2 + y, 1/2 − z; (viii) −1 − x, y, 1/2 − z.
Figure 1. View of the crystal structures of SrLnCuS3 (Ln = La, top-left; Nd, top-right, Tm, bottom) together with the coordination polyhedra formed by the metal ions. Color code: green polyhedron = (Sr1/La1)S7, (Sr1/Nd1)S7 and SrS6; blue polyhedron = (Sr2/La2)S7, (Sr2/Nd2)S7 and TmS6; burnt orange polyhedron = CuS4. Symmetry codes for SrLaCuS3: (i) x, –1 + y, z; (ii) 1/2 + x, −1/2 − y, 1/2 − z; (iii) 1/2 + x, 1/2 − y, 1/2 − z; (iv) 1/2 − x, −y, −1/2 + z; (v) 1/2 − x, 1 − y, −1/2 + z; (vi) −1/2 + x, 1/2 − y, 1/2 − z; (vii) x, 1 + y, z; (viii) 1 − x, 1/2 + y, −z; (ix) −1/2 + x, 1/2 − y, 1/2 − z. Symmetry codes for SrNdCuS3: (i) x, −1 + y, z; (ii) 1/2 − x, −y, 1/2 + z; (iii) 1/2 − x, −1 − y, 3/2 − z; (iv) −1/2 + x, −1/2 − y, 3/2 − z; (v) 1/2 + x, 1/2 − y, 3/2 − z; (vi) x, 1 + y, z; (vii) 1/2 + x, −1/2 − y, 3/2 − z. Symmetry codes for SrTmCuS3: (i) −x, −y, −z; (ii) −x, −y, −1/2 + z; (iii) 1 + x, y, z; (iv) 1 + x, −y, −z; (v) −1/2 − x, 1/2 + y, 1/2 − z; (vi) −1/2 + x, 1/2 + y, z; (vii) −3/2 − x, 1/2 + y, 1/2 − z; (viii) −1 − x, y, 1/2 − z.
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Figure 2. The IR (bottom) and Raman (top) spectra of SrLnCuS3 (Ln = Sr, Nd, Tm).
Figure 2. The IR (bottom) and Raman (top) spectra of SrLnCuS3 (Ln = Sr, Nd, Tm).
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Figure 3. The normalized Kubelka–Munk spectra of SrLaCuS3 (black), SrNdCuS3 (red) and SrTmCuS3 (blue). Sharp bands at about 1.30–1.80 and 2.06 in the spectrum of SrNdCuS3 correspond to different transitions of Nd3+ [53].
Figure 3. The normalized Kubelka–Munk spectra of SrLaCuS3 (black), SrNdCuS3 (red) and SrTmCuS3 (blue). Sharp bands at about 1.30–1.80 and 2.06 in the spectrum of SrNdCuS3 correspond to different transitions of Nd3+ [53].
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Figure 4. Field-dependent magnetic moments at 296 K (left), and temperature-dependent specific magnetization and reciprocal magnetic susceptibility (right) of SrNdCuS3 (top) and SrTmCuS3 (bottom) at 200 Oe. The temperature-dependent measurements were performed in the zero-field cooled (ZFC) and nonzero-field cooled (FC) modes.
Figure 4. Field-dependent magnetic moments at 296 K (left), and temperature-dependent specific magnetization and reciprocal magnetic susceptibility (right) of SrNdCuS3 (top) and SrTmCuS3 (bottom) at 200 Oe. The temperature-dependent measurements were performed in the zero-field cooled (ZFC) and nonzero-field cooled (FC) modes.
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Figure 5. Observed (blue), calculated (red) and difference (green) X-ray powder diffraction patterns for SrLnCuS3 after crystal structure refinement. Insets show the SEM images of SrLnCuS3.
Figure 5. Observed (blue), calculated (red) and difference (green) X-ray powder diffraction patterns for SrLnCuS3 after crystal structure refinement. Insets show the SEM images of SrLnCuS3.
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Table
Table 1. Experimental details for the structures of SrLnCuS3, solved from the single-crystal X-ray diffraction data.
Table 1. Experimental details for the structures of SrLnCuS3, solved from the single-crystal X-ray diffraction data.
SrLaCuS3 aSrNdCuS3 aSrNdCuS3 aSrYCuS3 aSrTmCuS3 aSrScCuS3 a
Space groupPnmaPnmaPnmaPnmaCmcmCmcm
Structural typeBa2MnS3BaLaCuS3Eu2CuS3Eu2CuS3KZrCuS3KZrCuS3
a (Å)8.1682(6)11.0663(8)10.5693(7)10.1845(7)3.9163(3)3.8316(3)
b (Å)4.0748(3)4.0886(3)4.0072(3)3.9378(3)12.9520(9)12.8504(9)
c (Å)16.0394(11)11.4625(8)12.8905(9)12.9426(9)10.0642(7)9.7153(7)
V (Å3)533.85(7)518.63(2)545.96(3)519.06(2)510.50(6)478.36(2)
Z444444
ρ (g cm−3)4.8065.0154.7644.3035.4164.059
μ (mm−1)22.7625.2023.9426.4132.8118.01
Collected reflection13821707410117849127564498
Unique reflections846678738734340351
Rint0.06530.0680.1370.0750.06780.055
R1(all)0.02170.0320.0430.0290.02480.017
wR2(all)0.03820.0540.0800.0330.04260.032
S1.0221.0591.0040.9411.0071.031
ReferenceThis work[46][46][47]This work[47]
a Heating a stoichiometric ratio of the elements Sr, Ln, Cu and S in the presence of CsBr as a flux in an evacuated quartz ampoule for 8 days at 1070–1120 K.
Table
Table 2. Experimental details for the structures of SrLnCuS3, solved from the powder X-ray diffraction data.
Table 2. Experimental details for the structures of SrLnCuS3, solved from the powder X-ray diffraction data.
SrLaCuS3 aSrLaCuS3 bSrCeCuS3 aSrCeCuS3 cSrPrCuS3 aSrNdCuS3 dSrSmCuS3 a
Space groupPnmaPnmaPnmaPnmaPnmaPnmaPnma
Structural typeBaLaCuS3Ba2MnS3BaLaCuS3Ba2MnS3BaLaCuS3BaLaCuS3Eu2CuS3
a (Å)11.2415(1)8.1746(3)11.1626(2)8.1393(3)11.1171(1)11.0815(2)10.4285(2)
b (Å)4.11053(6)4.0727(2)4.0970(2)4.0587(2)4.09492(6)4.0849(1)3.98640(7)
c (Å)11.5990(1)16.0473(8)11.5307(1)15.9661(2)11.5069(2)11.4684(2)12.9325(2)
V (Å3)535.97(1)534.26(4)527.33(1)527.44(2)523.84(1)519.14(1)537.63(2)
RDDM (%)5.255.734.526.615.034.004.94
RF (%)1.531.12.873.781.803.72.09
Impurity–2.6% SrS–––5.2% SrS
1.3% NdCuSO		2.6% SmCuS2
1.6% Sm2SO2
Reference[43]This work[44][44][43]This work[22]
SrGdCuS3 aSrHoCuS3 cSrErCuS3 aSrErCuS3 cSrTmCuS3 eSrYbCuS3 cSrLuCuS3 a
Space groupPnmaPnmaCmcmCmcmCmcmCmcmCmcm
Structural typeEu2CuS3Eu2CuS3KZrCuS3KZrCuS3KZrCuS3KZrCuS3KZrCuS3
a (Å)10.3288(2)10.1487(1)3.92672(5)3.93128(3)3.9210(1)3.91448(4)3.91105(4)
b (Å)3.96271(7)3.9332(1)12.9632(2)12.9709(1))12.9523(5)12.9554(1)12.9504(1)
c (Å)12.9397(2)12.9524(2)10.0974(1)10.1161(1)10.0687(4)10.0332(1)10.0206(1)
V (Å3)529.62(2)517.02(2)513.99(1)515.843(9)511.34(3)508.842(8)507.540(8)
RDDM (%)4.414.295.673.734.803.565.27
RF (%)2.181.912.602.062.601.481.27
Impurity3.6% GdCuS2
2.5% SrS
0.8% Gd2SO2		2.6% SrS6.3% ErxCuyS2
3.5% SrS		9.5% Er2SO2
1.2% SrS
0.5% Er5S(SiO4)3		5.1% Tm2SO2
1.2% SrS		2.2% Yb2SO2
1.8% Yb5S(SiO4)3
1.2% SrS		1.6% SrS
1.1% Lu2SO2
Reference[22][36][22][45]This work[45][22]
a Melting of sulfides Cu2S, Ln2S3 and SrS under a high-frequency current condition, followed by annealing at 970 K for 3 months. b Sulfidation of oxides (Sr0.15La1.85)CuO4, (Sr0.05La1.95)CuO4, SrLnCuO4 obtained by thermal decomposition of nitrates, at 1170 K. c Melting of sulfides Cu2S, Ln2S3 and SrS under a high-frequency current condition, followed by annealing at 1170 K for 2 months. d Sulfidation of oxides Nd2O3, Sr2CuO4 and Nd2CuO4, obtained by thermal decomposition of nitrates, at 1170 K. e Sulfidation of oxides SrTm2O4, Tm2O3, Sr2CuO4, Tm2CuO4 and CuSrO2, obtained by thermal decomposition of nitrates, at 1170 K.
Table
Table 3. Fractional atomic coordinates and occupancy of SrLnCuS3 (Ln = La, Nd, Tm).
Table 3. Fractional atomic coordinates and occupancy of SrLnCuS3 (Ln = La, Nd, Tm).
AtomxyzOccupancyxyzOccupancy
SrLaCuS3 (single crystal)SrLaCuS3 (powdered sample)
Sr10.09058(3)1/40.785319(17)0.502(5)0.09026(6)1/40.785177(28)0.5453(46)
La10.09058(3)1/40.785319(17)0.498(5)0.09026(6)1/40.785177(28)0.4547(46)
Sr20.25439(3)1/40.038345(17)0.489(6)0.25446(6)1/40.038210(26)0.4550(43)
La20.25439(3)1/40.038345(17)0.511(6)0.25446(6)1/40.038210(26)0.5450(43)
Cu0.11864(6)1/40.36655(3)10.11857(11)1/40.36652(6)1
S10.17928(12)1/40.22120(6)10.17956(18)1/40.22114(9)1
S20.38083(12)1/40.42864(6)10.38097(19)1/40.42837(10)1
S30.01190(12)1/40.60039(6)10.01197(18)1/40.60006(10)1
SrNdCuS3 (single crystal) [46]SrNdCuS3 (powdered sample)
Sr10.31732(6)1/40.49523(6)10.31752(15)1/40.49500(17)0.886(5)
Nd10.48946(3)1/40.81684(4)10.31752(15)1/40.49500(17)0.114(5)
Sr2––––0.48947(13)1/40.81683(11)0.114(5)
Nd2––––0.48947(13)1/40.81683(11)0.886(5)
Cu0.24480(8)1/40.21334(9)10.2447(2)1/40.2133(3)1
S10.22363(17)1/40.80669(16)10.2250(5)1/40.8076(4)1
S20.04818(16)1/40.14176(17)10.0487(4)1/40.1406(4)1
S30.38733(17)1/40.05848(17)10.3872(4)1/40.0571(4)1
SrTmCuS3 (single crystal)SrTmCuS3 (powdered sample)
Sr00.74817(7)1/4100.74800(12)1/41
Tm00010001
Cu00.47124(9)1/4100.47147(17)1/41
S100.36340(13)0.06401(14)100.3634(2)0.0644(2)1
S200.07621(18)1/4100.0761(3)1/41
Table
Table 4. Bond lengths (Å) in the crystal structures of SrLnCuS3 (Ln = La, Nd, Tm). For symmetry codes see Figure 1.
Table 4. Bond lengths (Å) in the crystal structures of SrLnCuS3 (Ln = La, Nd, Tm). For symmetry codes see Figure 1.
SrLaCuS3 (Single Crystal/Powdered Sample)
Sr1/La1–S12.957(1)/2.9569(11)Sr2/La2–S12.996(1)/2.9988(16)Cu–S12.383(1)/2.3857(18)
Sr1/La1–S1i2.957(1)/2.9569(11)Sr2/La2–S2iv2.910(1)/2.9119(12)Cu–S2x2.362(1)/2.3636(18)
Sr1/La1–S1ii3.003(1)/3.0036(11)Sr2/La2–S2v2.910(1)/2.9119(12)Cu–S3vi2.360(1)/2.3607(9)
Sr1/La1–S1iii3.003(1)/3.0036(11)Sr2/La2–S2vi3.097(1)/3.0999(17)Cu–S3ix2.360(1)/2.3607(9)
Sr1/La1–S23.081(1)/3.0793(13)Sr2/La2–S32.964(1)/2.9627(11)
Sr1/La1–S2i3.081(1)/3.0793(13)Sr2/La2–S3vii2.964(1)/2.9627(11)
Sr1/La1–S33.035(1)/3.0387(16)Sr2/La2–S3viii3.062(1)/3.0585(16)
SrNdCuS3 (Single Crystal/Powdered Sample)
Sr1/Nd1–S13.009(2)/3.002(4)Sr2/Nd2–S12.944(2)/2.933(5)Cu–S12.334(1)/2.335(3)
Sr1/Nd1–S1i3.009(2)/3.002(4)Sr2/Nd2–S1v2.953(2)/2.974(5)Cu–S1i2.334(1)/2.335(3)
Sr1/Nd1–S2ii3.036(2)/3.026(4)Sr2/Nd2–S22.895(1)/2.904(4)Cu–S22.325(2)/2.327(5)
Sr1/Nd1–S2iii3.036(2)/3.026(4)Sr2/Nd2–S2vi2.895(1)/2.904(4)Cu–S32.375(2)/2.388(5)
Sr1/Nd1–S2iv2.999(2)/2.997(5)Sr2/Nd2–S3ii2.992(2)/2.980(5)
Sr1/Nd1–S3ii3.136(2)/3.135(4)Sr2/Nd2–S3v2.843(1)/2.851(3)
Sr1/Nd1–S3iii3.136(2)/3.135(4)Sr2/Nd2–S3vii2.843(1)/2.851(3)
SrTmCuS3 (Single Crystal/Powdered Sample)
Sr–S1ii3.093(1)/3.093(2)Tm–S12.717(1)/2.719(2)Cu–S12.336(2)/2.335(3)
Sr–S1v3.093(1)/3.093(2)Tm–S1i2.717(1)/2.719(2)Cu–S1viii2.336(2)/2.335(3)
Sr–S1vi3.093(1)/3.093(2)Tm–S1iii2.717(1)/2.719(2)Cu–S22.384(2)/2.383(3)
Sr–S1vii3.093(1)/3.093(2)Tm–S1iv2.717(1)/2.719(2)Cu–S2i2.384(2)/2.383(3)
Sr–S22.966(2)/2.966(3)Tm–S22.703(1)/2.703(2)
Sr–S2i2.966(2)/2.966(3)Tm–S2ii2.703(1)/2.703(2)
Table
Table 5. Magnetic characteristics for SrNdCuS3 and SrTmCuS3.
Table 5. Magnetic characteristics for SrNdCuS3 and SrTmCuS3.
SrNdCuS3SrTmCuS3
Space groupPnmaCmcm
Structural typeBa2MnS3KZrCuS3
Calculated μ (μB)3.6187.561
Experimental μ296 K (μB)3.6117.378
Experimental μ20–300 K (μB)3.527.57
Calculated C (K m3 kmol−1)0.020570.08983
Experimental C20–300 K (K m3 kmol−1)0.01950.0901
Experimental θ20–300 K (K)−18−12
Table
Table 6. The calculated and found elemental analysis data for SrLnCuS3 (Ln = La, Nd, Tm) obtained using SEM-EDX.
Table 6. The calculated and found elemental analysis data for SrLnCuS3 (Ln = La, Nd, Tm) obtained using SEM-EDX.
Compound (Mass)Calculated (%)Found (%)
SrLnCuSOSrLnCuSO
SrLaCuS3 (386.25)22.6835.9616.4524.90–23.2335.8216.0624.89–
97.4% SrLaCuS3 + 2.6% SrS23.1035.6716.3224.92–
SrNdCuS3 (391.59)22.3836.8316.2324.56–24.6835.1815.5224.540.08
93.5% SrNdCuS3 + 5.2% SrS + 1.3% NdCuSO23.0236.4016.0424.490.06
SrTmCuS3 (416.28)21.0540.5815.2723.10–20.5342.5114.2522.300.41
93.7% SrTmCuS3 + 1.2% SrS + 5.1% Tm2SO220.1842.6014.4522.360.40
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Ruseikina, A.V.; Grigoriev, M.V.; Solovyov, L.A.; Chernyshev, V.A.; Aleksandrovsky, A.S.; Krylov, A.S.; Krylova, S.N.; Shestakov, N.P.; Velikanov, D.A.; Garmonov, A.A.; et al. A Challenge toward Novel Quaternary Sulfides SrLnCuS3 (Ln = La, Nd, Tm): Unraveling Synthetic Pathways, Structures and Properties. Int. J. Mol. Sci. 2022, 23, 12438. https://doi.org/10.3390/ijms232012438

AMA Style

Ruseikina AV, Grigoriev MV, Solovyov LA, Chernyshev VA, Aleksandrovsky AS, Krylov AS, Krylova SN, Shestakov NP, Velikanov DA, Garmonov AA, et al. A Challenge toward Novel Quaternary Sulfides SrLnCuS3 (Ln = La, Nd, Tm): Unraveling Synthetic Pathways, Structures and Properties. International Journal of Molecular Sciences. 2022; 23(20):12438. https://doi.org/10.3390/ijms232012438

Chicago/Turabian Style

Ruseikina, Anna V., Maxim V. Grigoriev, Leonid A. Solovyov, Vladimir A. Chernyshev, Aleksandr S. Aleksandrovsky, Alexander S. Krylov, Svetlana N. Krylova, Nikolai P. Shestakov, Dmitriy A. Velikanov, Alexander A. Garmonov, and et al. 2022. "A Challenge toward Novel Quaternary Sulfides SrLnCuS3 (Ln = La, Nd, Tm): Unraveling Synthetic Pathways, Structures and Properties" International Journal of Molecular Sciences 23, no. 20: 12438. https://doi.org/10.3390/ijms232012438

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