Cationic Control of the Formation of Europium Carbodiimide Chlorides

Abstract The solid‐state syntheses and the structures of three new europium carbodiimide chlorides are reported: Eu 4 (NCN) 3 Cl 3 =Eu (3+) Eu 3 (2+) (NCN) 3 Cl 3 ( 1 ), LiEu 2 (NCN)Cl 3 ( 2 ) and Na 2 Eu 14 (NCN) 3 Cl 24 ( 3 ). 1 is the second example of mixed‐valent rare‐earth carbodiimide after Eu 4 F 5 (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.