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

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.