Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs 2 NaLn(PS 4 ) 2 (Ln = La-Nd, Sm, and Gd-Ho)

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 Cs NaLn(PS ) (Ln = La-Nd, Sm, and Gd-Ho) were grown as large single crystals (∼0.1-1 mm ) 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 Cs NaLn(PS ) series crystallize in the same space group and have the same Wyckoff atom positions, a slight change in size between Sm and Gd 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 Cs NaLn(PS ) (Ln = Ce, Pr, Nd, Gd, and Tb) compounds revealed paramagnetic behavior.