Synthesis and Characterization of the First Tetracyanamidogallate

Abstract

A tetracyanamidogallate with the formula LiSr2[Ga(CN2)4] was prepared from stoichiometric mixtures of SrF2, GaF3, and Li2(CN2) in a fused silica tube. The formation of LiSr2[Ga(CN2)4] by solid‐state metathesis was studied by differential scanning calorimetry. A crystalline powder of LiSr2[Ga(CN2)4] was studied by X‐ray powder diffraction, and powder patterns were indexed isotypically to LiSr2[Al(CN2)4]. The crystal structure of LiSr2[Ga(CN2)4] was refined by single‐crystal X‐ray diffraction, thus indicating a disorder of Li+ and Ga3+ ions that was investigated by the means of 71Ga solid‐state magic‐angle spinning (MAS) NMR spectroscopic measurements and DFT calculations.

Synthesis, Crystal Structure, and Chemical-Bonding Analysis of BaZn(NCN)2

“…Very recently, we have come close in this endeavor with the preparation of SrZn(NCN) 2 [14], the first example of a ternary post-transition metal carbodiimide, which was targeted with inspiration from LiSr 2 M(NCN) 4 (M = Al 3+ and Ga 3+ ) phases [15,16]. SrZn(NCN) 2 adopts the versatile BaZnOS structure which, in oxychalcogenide analogues, can incorporate a range of different tetrahedrally coordinated divalent transition metals [17,18].…”

Synthesis, Luminescence and Nonlinear Optical Properties of Homoleptic Tetracyanamidogermanates ARE[Ge(CN2)4] (A = K, Cs, and RE = La, Ce, Pr, Nd, Sm, Eu, Gd)

“…The nearly tetrahedral environment of tetracyanamidometallates with the penetrating orientation of the cyanamido ligand is rarely seen in structures of carbodiimides, where a closest stick packing of linear (NCN) units usually introduces layered arrangements of structures ,. [9b], ,…”

“…ARE [Si(CN 2 ) 4 ] ( A = alkali, RE = rare earth) compounds appear chemically highly inert and Ln ‐doped ( Ln = Ce, Eu, Tb) compounds have shown remarkable photoluminescence properties . Since then, the group of cyanamidometallates was attributed with new representatives (Table ), such as aluminates Li EA 2 [Al(CN 2 ) 4 ], gallates LiSr 2 [Ga(CN 2 ) 4 ], and germanates ARE [Ge(CN 2 ) 4 ] …”

Eu2(CN2)3 and KEu[Si(CN2)4]: Missing Members of the Rare Earth Metal Carbodiimide and Tetracyanamidosilicate Series

“…The first tetracyanamidometallate was obtained with the [Si(CN 2 ) 4 ] 4– ion, which can be derived from orthosilicates by substituting the oxygen atoms with [N–C–N] units . Recently, other tetracyanamidometallates such as [M(CN 2 ) 4 ] (M = Al, Ge, and Ga) were reported . The synthesis of potassium tetracyanamidosilicates was successful for large RE ions, from La to Gd, albeit without Eu.…”

“…[7] Recently, other tetracyanamidometallates such as [M(CN 2 ) 4 ] (M = Al, Ge, and Ga) were reported. [8][9][10] The synthesis of potassium tetracyanamidosilicates was successful for large RE ions, from La to Gd, [7] albeit without Eu. The synthesis of potassium tetracyanamidosilicates with REs smaller than Gd were not successful because of the competing quasibinary carbodiimides.…”