Department of Chemistry, Florida State University , Tallahassee Florida 32308, United States.
J Am Chem Soc. 2016 Aug 24;138(33):10636-44. doi: 10.1021/jacs.6b06024. Epub 2016 Aug 16.
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(LixFe1-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 (Eg = 2.5 eV). Ca6(LixFe1-x)Te2N3 features isolated linear N-Fe-N units with iron in the rare Fe(1+) state. The magnetic behavior of the iron site was characterized by magnetic susceptibility measurements, which indicate a very high magnetic moment (5.16μB) 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.
两种新的含碲氮化物是通过熔融钙和锂的反应生长出来的。化合物 Ca6Te3N2 结晶于 R3̅c 空间群（a = 12.000(3)Å, c = 13.147(4)Å; Z = 6）; 其结构是 rinneite (K3NaFeCl6) 的反型和 2H 钙钛矿相关氧化物，如 Sr3Co2O6。化合物 Ca6(LixFe1-x)Te2N3（其中 x ≈ 0.48）形成于 P42/m 空间群（a = 8.718(3)Å, c = 6.719(2)Å; Z = 2），具有 Tl3BiCl6 结构的新型填充反型变体。能带结构计算和易于观察的红/绿二色性表明 Ca6Te3N2 是一种各向异性的直接带隙半导体（Eg = 2.5 eV）。Ca6(LixFe1-x)Te2N3 具有孤立的线性 N-Fe-N 单元，其中铁处于罕见的 Fe(1+)态。通过磁性测量研究了铁位的磁性行为，这表明铁的磁矩非常高（5.16μB），可能是由于自旋轨道耦合程度很高。Fe/Li 混合位的固有无序阻碍了磁中心之间的长程相互作用。
