Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs2NaLn(PS4)2 (Ln = La-Nd, Sm, and Gd-Ho).

Abstract

The effect of lanthanide contraction often results in topological and symmetry changes in compounds with the same compositions as a function of lanthanide cation size. Here we report on the first example of a lanthanide thiophosphate exhibiting a change in the lanthanide cation environment without any topological or symmetry change. A series of new lanthanide thiophosphates with mixed alkali cations were obtained via a flux crystal growth technique using a CsI flux. The obtained compounds Cs2NaLn(PS4)2 (Ln = La-Nd, Sm, and Gd-Ho) were grown as large single crystals (∼0.1-1 mm3) and characterized using single-crystal X-ray diffraction and magnetic susceptibility measurements. As we moved across the series, the structural studies revealed a change in the lanthanide coordination environment depending on the identity of the lanthanide. Although all compounds in the Cs2NaLn(PS4)2 series crystallize in the same space group and have the same Wyckoff atom positions, a slight change in size between Sm3+ and Gd3+ causes a subtle change in coordination number from 9 (for Ln = La-Sm) to 8 (for Ln = Gd-Ho), resulting in two distinct but virtually identical structure types. Ab initio calculations were performed, and the observed experimental trend was corroborated computationally. Magnetic measurements performed on the Cs2NaLn(PS4)2 (Ln = Ce, Pr, Nd, Gd, and Tb) compounds revealed paramagnetic behavior.