Cationic Control of the Formation of Europium Carbodiimide Chlorides.

The solid‐state syntheses and the structures of three new europium carbodiimide chlorides are reported: Eu4(NCN)3Cl3=Eu(3+)Eu3(2+)(NCN)3Cl3 (1), LiEu2(NCN)Cl3 (2) and Na2Eu14(NCN)3Cl24 (3). 1 is the second example of mixed‐valent rare‐earth carbodiimide after Eu4F5(NCN)2. 2 belongs to a group of mixed carbodiimide compounds related to the Bideauxite group. 3 being the first Na‐containing rare‐earth carbodiimide. Syntheses in the field of rare‐earth carbodiimides benefit from the usage of different alkali carbodiimides to direct reaction pathway into individual compounds. High‐yield syntheses of 1–3, their crystal structures, and the photoluminescence properties of 3 are reported. [ABSTRACT FROM AUTHOR]