Laboratory of Theory and Optimization of Chemical and Technological Processes, University of Tyumen, 625003 Tyumen, Russia.
Federal Research Center KSC SB RAS, Institute of Chemistry and Chemical Technology, 660036 Krasnoyarsk, Russia.
Int J Mol Sci. 2022 Oct 18;23(20):12438. doi: 10.3390/ijms232012438.
We report on the novel heterometallic quaternary sulfides SrLnCuS (Ln = La, Nd, Tm), obtained as both single crystals and powdered samples. The structures of both the single crystal and powdered samples of SrLaCuS and SrNdCuS belong to the orthorhombic space group but are of different structural types, while both samples of SrTmCuS crystallize in the orthorhombic space group with the structural type KZrCuS. Three-dimensional crystal structures of SrLaCuS and SrNdCuS are formed from the (Sr/Ln)S capped trigonal prisms and CuS tetrahedra. In SrLaCuS, alternating 2D layers are stacked, while the main backbone of the structure of SrNdCuS is a polymeric 3D framework [(Sr/Ln)S], strengthened by 1D polymeric chains (CuS) with 1D channels, filled by the other Sr/Ln cations, which, in turn, form 1D dimeric ribbons. A 3D crystal structure of SrTmCuS is constructed from the SrS trigonal prisms, TmS octahedra and CuS tetrahedra. The latter two polyhedra are packed together into 2D layers, which are separated by 1D chains (SrS) and 1D free channels. In both crystal structures of SrLaCuS obtained in this work, the crystallographic positions of strontium and lanthanum were partially mixed, while only in the structure of SrNdCuS, solved from the powder X-ray diffraction data, were the crystallographic positions of strontium and neodymium partially mixed. Band gaps of SrLnCuS (Ln = La, Nd, Tm) were found to be 1.86, 1.94 and 2.57 eV, respectively. Both SrNdCuS and SrTmCuS were found to be paramagnetic at 20-300 K, with the experimental magnetic characteristics being in good agreement with the corresponding calculated parameters.
我们报告了新型杂金属四元硫化物 SrLnCuS（Ln = La、Nd、Tm），它可以作为单晶和粉末样品获得。SrLaCuS 和 SrNdCuS 的单晶和粉末样品的结构均属于正交空间群 ，但结构类型不同，而 SrTmCuS 的两个样品均结晶在正交空间群 中，结构类型为 KZrCuS。SrLaCuS 和 SrNdCuS 的三维晶体结构由（Sr/Ln）S 封端的三角棱柱和 CuS 四面体组成。在 SrLaCuS 中，交替的 2D 层堆叠，而 SrNdCuS 结构的主要骨架是聚合的 3D 框架[(Sr/Ln)S]，由 1D 聚合链（CuS）增强，1D 通道填充其他 Sr/Ln 阳离子，它们反过来形成 1D 二聚体带。SrTmCuS 的 3D 晶体结构由 SrS 三角棱柱、TmS 八面体和 CuS 四面体组成。后两种多面体被包装成 2D 层，由 1D 链（SrS）和 1D 自由通道隔开。在本工作中获得的 SrLaCuS 的两个晶体结构中，锶和镧的晶体位置部分混合，而只有在从粉末 X 射线衍射数据中解决的 SrNdCuS 结构中，锶和钕的晶体位置部分混合。SrLnCuS（Ln = La、Nd、Tm）的带隙分别为 1.86、1.94 和 2.57 eV。SrNdCuS 和 SrTmCuS 在 20-300 K 下均表现为顺磁性，实验磁性特征与相应的计算参数非常吻合。
