Exploring New Zintl Phases in the 9-4-9 Family via Al Substitution. Synthesis, Structure, and Physical Properties of Ae(9)Mn(4-x)Al(x)Sb(9) (Ae = Ca, Yb, Eu)
Exploring New Zintl Phases in the 9-4-9 Family via Al Substitution. Synthesis, Structure, and Physical Properties of Ae(9)Mn(4-x)Al(x)Sb(9) (Ae = Ca, Yb, Eu)
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通过 Al 替代探索 9-4-9 系列中的新 Zintl 阶段。
DOI：
10.1021/acs.inorgchem.9b03320
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发表时间：
2020
影响因子：
4.6
通讯作者：
Xia Sheng-Qing
中科院分区：
文献类型：
--
作者：
Liu Xiao-Cun;Liu Ke-Feng;Wang Qi-Qi;Wang Yan-Min;Pan Ming-Yan;Xia Sheng-Qing
Three new quaternary Zintl phases with the “9-4-9” formula, Ae9Mn4–xAlxSb9(Ae = Ca, Yb, Eu), have been synthesized using Pb as the metal flux, and their crystal structures have been established by single-crystal X-ray diffraction. Both Ca9Mn2.91(4)Al1.09Sb9and Yb9Mn3.59(6)Al0.41Sb9are isostructural with Ca9Mn4Bi9, and they crystallize in the orthorhombic space groupPbamwith unit cell dimensions ofa= 12.4571(8), 12.2884(16) Å,b= 22.1352(16), 22.024(3) Å, andc= 4.6012(3), 4.6187(6) Å, respectively. Their anionic structures can be viewed as infinite ribbons based on corner-shared tetrahedrons. Also, Eu9Mn2.87(4)Al1.13Sb9has the space groupCmcaanda= 9.4883(7) Å,b= 23.6895(18) Å, andc= 24.4845(19) Å. The structural relationships between Ca9Mn2.91(4)Al1.09Sb9and Eu9Mn2.87(4)Al1.13Sb9are compared and discussed as well. The successful Al3+substitution provides additional electrons to the compounds to achieve structural stability. Magnetic susceptibility and electrical resistivity measurements, performed on single crystals of Eu9Mn2.87(4)Al1.13Sb9, indicate complex magnetic properties and semiconductor behavior. The physical properties of Yb9Mn3.59(6)Al0.41Sb9are similar to those observed for Yb9Mn4.18(2)Sb9.
