Dimensional reduction upon calcium incorporation in Cs0.3(Ca0.3Ln0.7)PS4 and Cs0.5(Ca0.5Ln0.5)PS4†
Abstract
Two series of new lanthanide thiophosphates with partial Ca occupancy of the Ln sites, Cs0.3(Ca0.3Ln0.7)PS4 (Ln = Ce, Pr, Nd, Sm, Gd, Tb, and Dy) and Cs0.5(Ca0.5Ln0.5)PS4 (Ln = Pr, Nd, Sm, Gd, and Tb), were synthesized using a CsI flux and structurally characterized. The first series with an idealized formula of Cs0.3(Ca0.3Ln0.7)PS4 crystallizes in the Rm space group and belongs to a new structure type that consists of a channel containing [(Ca0.3Ln0.7)PS4]0.3− framework, where the channels are occupied by severely disordered Cs+ cations. A second new series with formula Cs0.5(Ca0.5Ln0.5)PS4 crystallizes in the monoclinic C2/c space group and exhibits a layered structure consisting of [(Ca0.5Ln0.5)PS4]0.5− layers with Cs+ cations located between the layers for charge balance. Together with the parent structure type, LnPS4, these three structure types illustrate how the LnPS4 structure changes with Cs+ cation incorporation, reducing its dimensionality from 3D to 2D. The magnetic properties of Cs0.3[(Ca0.3Ce0.7)PS4] and Cs0.3[(Ca0.3Pr0.7)PS4] were studied and revealed no magnetic transition down to 2 K.
- This article is part of the themed collection: Crystal Engineering Techniques