Crystal structure, magnetic and photoluminescence properties of GdW${}_6$Cl${}_{15}$, TbW${}_6$Cl${}_{15}$, and EuW${}_6$Cl${}_{14}$

Ternary compounds with the [M${}_6$X${}_{14}$]${}^{2-}$ (M=Mo, W; X=Cl, Br, I) cluster have been established with several counter cations. Herein, we report examples of the ternary rare-earth (RE) compounds REW${}_6$Cl${}_{15}$ and RE${}_6$Cl${}_{14}$. Preparations of the compounds GdW${}_6$Cl${}_{15}$, TbW${}_6$Cl${}_{15}$, and EuW${}_6$Cl${}_{14}$ are accomplished by solid-state reactions of W${}_6$Cl${}_{12}$ and RECl${}_3$ (RE=Gd, Tb), or EuCl${}_2$ at 575 °C in fused silica tubing. GdW${}_6$Cl${}_{15}$ and TbW${}_6$Cl${}_{15}$ crystallize in the space group C2/c and EuW${}_6$Cl${}_{14}$ in Pn$\overline{3}$, isotypic to BiW${}_6$Cl${}_{15}$ (RE${}_6$Cl${}_{15}$) and PbMo${}_6$Cl${}_{15}$ (EuW${}_6$Cl${}_{14}$) according to X-ray powder diffraction. Crystal structures are discussed in the light of related compounds, and properties such as magnetism and photoluminescence are reported. (© 2021 The Authors. Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH)