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

• Published in: International journal of molecular sciences Vol. 23; no. 20; p. 12438
• Main Authors: Ruseikina, Anna V., Grigoriev, Maxim V., Solovyov, Leonid A., Chernyshev, Vladimir A., Aleksandrovsky, Aleksandr S., Krylov, Alexander S., Krylova, Svetlana N., Shestakov, Nikolai P., Velikanov, Dmitriy A., Garmonov, Alexander A., Matigorov, Alexey V., Eberle, Marcel A., Schleid, Thomas, Safin, Damir A.
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 18.10.2022; MDPI
• Subjects: ab initio calculations; Cations; Channels; Crystal structure; Crystallography; Crystals; inorganic materials; Lanthanum; magnetic measurements; Magnetic properties; Neodymium; Nitrates; Prisms; quaternary sulfide; Single crystals; Strontium; Sulfides; synthesis; X ray powder diffraction; X-ray diffraction
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms232012438

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.