Syntheses, Crystal and Electronic Structures, and Physical Properties of Quaternary Semiconductors: Ln2Mn3Sb4S12 (Ln = Pr, Nd, Sm, Gd)
journal contributionposted on 05.07.2010 by Hua-Jun Zhao, Long-Hua Li, Li-Ming Wu, Ling Chen
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Four new quaternary lanthanide antimony sulfides: Ln2Mn3Sb4S12 (Ln = Pr, Nd, Sm, Gd) have been synthesized from a stoichiometric element mixture at 1373 K by conventional solid state reactions. These compounds crystallize in the monoclinic space group C2/m with the unit cell parameters of a = 19.928(2)−19.9672(6) Å, b = 3.9323(4)−3.8803(2) Å, c = 14.921(2)−14.9011(1) Å, V = 938.5(2)−925.63(6) Å3, and Z = 2 on going from Ln = Pr to Gd. Their structure represents a novel wavy MnS6 octahedron layer decorated on both sides by chains of an SbS5 square pyramid via strong Sb−S bonding interactions (< 3.0 Å). Such a MnS6 octahedron layer consists of chains of an edge-sharing [Mn1S6]2 dimer extending along  that are interconnected by single strings of an edge-sharing Mn2S6 octahedron at axial S apexes. Sm2Mn3Sb4S12 displays spin-canted antiferromagnetic interactions between Sm2+ and Mn2+ centers and an optical gap of 1.50 eV. The DFT study indicates an indirect band gap with an electronic transfer excitation of S 3p to Sb 5p orbital electrons.