Exploring New Zintl Phases in the 9-4-9 Family via Al Substitution. Synthesis, Structure, and Physical Properties of Ae9Mn4- xAlxSb9 (Ae = Ca, Yb, Eu)

Xiao-Cun Liu; Ke-Feng Liu; Qi-Qi Wang; Yan-Min Wang; Ming-Yan Pan; Sheng-Qing Xia

doi:10.1021/acs.inorgchem.9b03320

Exploring New Zintl Phases in the 9-4-9 Family via Al Substitution. Synthesis, Structure, and Physical Properties of Ae₉Mn_{4- x}Al_xSb₉ (Ae = Ca, Yb, Eu)

Inorg Chem. 2020 Mar 16;59(6):3709-3717. doi: 10.1021/acs.inorgchem.9b03320. Epub 2020 Feb 25.

Authors

Xiao-Cun Liu¹, Ke-Feng Liu², Qi-Qi Wang², Yan-Min Wang¹, Ming-Yan Pan³, Sheng-Qing Xia²

Affiliations

¹ School of Civil Engineering, Shandong Jiaotong University, Jinan, Shandong 250023, People's Republic of China.
² State Key Laboratory of Crystal Materials, Institute of Crystal Materials, Shandong University, Jinan, Shandong 250100, People's Republic of China.
³ Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Science,Shanghai 201800, People's Republic of China.

PMID: 32096622
DOI: 10.1021/acs.inorgchem.9b03320

Abstract

Three new quaternary Zintl phases with the "9-4-9" formula, Ae₉Mn_4-xAl_xSb₉ (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 Ca₉Mn_2.91(4)Al_1.09Sb₉ and Yb₉Mn_3.59(6)Al_0.41Sb₉ are isostructural with Ca₉Mn₄Bi₉, and they crystallize in the orthorhombic space group Pbam with unit cell dimensions of a = 12.4571(8), 12.2884(16) Å, b = 22.1352(16), 22.024(3) Å, and c = 4.6012(3), 4.6187(6) Å, respectively. Their anionic structures can be viewed as infinite ribbons based on corner-shared tetrahedrons. Also, Eu₉Mn_2.87(4)Al_1.13Sb₉ has the space group Cmca and a = 9.4883(7) Å, b = 23.6895(18) Å, and c = 24.4845(19) Å. The structural relationships between Ca₉Mn_2.91(4)Al_1.09Sb₉ and Eu₉Mn_2.87(4)Al_1.13Sb₉ are 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 Eu₉Mn_2.87(4)Al_1.13Sb₉, indicate complex magnetic properties and semiconductor behavior. The physical properties of Yb₉Mn_3.59(6)Al_0.41Sb₉ are similar to those observed for Yb₉Mn_4.18(2)Sb₉.