Metal Nitrides Grown from Ca/Li Flux: Ca6Te3N2 and New Nitridoferrate(I) Ca6(LixFe1–x)Te2N3

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• 作者：Matthew J. Dickman ; Susan E. Latturner
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 24, 2016
• 年：2016
• 卷：138
• 期：33
• 页码：10636-10644
• 全文大小：543K
• 年卷期：0
• ISSN：1520-5126

文摘

Two new tellurium-containing nitrides were grown from reactions in molten calcium and lithium. The compound Ca₆Te₃N₂ crystallizes in space group R3̅c (a = 12.000(3)Å, c = 13.147(4)Å; Z = 6); its structure is an anti-type of rinneite (K₃NaFeCl₆) and 2H perovskite related oxides such as Sr₃Co₂O₆. The compound Ca₆(Li_xFe_1–x)Te₂N₃ where x ≈ 0.48 forms in space group P4₂/m (a = 8.718(3)Å, c = 6.719(2)Å; Z = 2) with a new stuffed anti-type variant of the Tl₃BiCl₆ structure. Band structure calculations and easily observable red/green dichroic behavior indicate that Ca₆Te₃N₂ is a highly anisotropic direct band gap semiconductor (E_g = 2.5 eV). Ca₆(Li_xFe_1–x)Te₂N₃ features isolated linear N–Fe–N units with iron in the rare Fe¹⁺ state. The magnetic behavior of the iron site was characterized by magnetic susceptibility measurements, which indicate a very high magnetic moment (5.16μ_B) likely due to a high degree of spin–orbit coupling. Inherent disorder at the Fe/Li mixed site frustrates long-range communication between magnetic centers.