Ba4FeCuS6:一种新的混合金属硫化物,具有包含稀有 CuS3 单元的伪零维结构†。

IF 2.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Sambit S. S. Rout, Gopabandhu Panigrahi, Sweta Yadav, K. V. Ramanujachary and Jai Prakash
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引用次数: 0

摘要

在此,我们介绍了利用两种方法合成新型混合过渡金属硫化物 Ba4FeCuS6 的过程:(a) 元素在真空中的高温反应;(b) 金属氧化物和碳酸盐在流动 CS2 中的高温反应。这两种方法都成功地生成了季硫化物的多晶相。用铅通量加热多晶样品,然后缓慢冷却反应混合物,就制备出了标题相的单晶体。Ba4FeCuS6 结构采用单斜晶系(空间群:P21/n)。考虑到结构中的铁(III)物种,硫化物原子电荷的划分很容易做到,即[Ba(II)]4[Fe(III)][Cu(I)][S(-II)]6。结构中的铜原子(Cu1 和 Cu2)分布在两个不同的位置。四个硫原子与每个铁原子成键,形成一个扭曲的四面体几何结构。相比之下,每个 Cu 原子的配位多面体中只有三个 S 原子,以稳定 S 原子的三棱平面几何。FeS4 和 Cu1(S3)/Cu2(S3) 多面体单元通过共角相互连接,形成阴离子假零维单元。Ba(II)阳离子中和了这些[FeCu1-xS6](x+8)-单元上的负电荷。每个 Ba 原子都被七个 S 原子包围,形成扭曲的单帽三棱柱几何形状。多晶 Ba4FeCuS6 是半导体,直接带隙为 1.06(2) eV。由于 Ba4FeCuS6 是直接带隙半导体(Eg ∼ 1 eV),因此未来对其光伏特性的探索将十分有趣。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Ba4FeCuS6: a new mixed metal sulfide with a pseudo-zero-dimensional structure containing rare CuS3 units†

Ba4FeCuS6: a new mixed metal sulfide with a pseudo-zero-dimensional structure containing rare CuS3 units†

Herein, we describe the synthesis of a new mixed transition metal sulfide, Ba4FeCuS6, using two methods: (a) the high-temperature reaction of elements under vacuum and (b) the reaction of metal oxides and carbonates under flowing CS2 at high temperatures. Both methods successfully produced polycrystalline phases of the quaternary sulfide. Single crystals of the title phase were prepared by heating the polycrystalline sample with a Pb flux followed by slow cooling of the reaction mixture. The Ba4FeCuS6 structure adopts the monoclinic crystal system (space group: P21/n). The partitioning of the atomic charges of the sulfide can be easily done considering the Fe(III) species in the structure, i.e., [Ba(II)]4[Fe(III)][Cu(I)][S(−II)]6. The Cu atoms, Cu1 and Cu2, of the structure are distributed at two split positions. Four sulfur atoms are bonded to each Fe atom, forming a distorted tetrahedral geometry. In contrast, only three S atoms are part of the coordination polyhedron of each Cu atom to stabilize the trigonal planar geometry of the S atoms. The FeS4 and Cu1(S3)/Cu2(S3) polyhedral units are interconnected by corner sharing to create anionic pseudo-zero-dimensional units. The Ba(II) cations neutralize the negative charges on these [FeCu1–xS6](x+8)− units. Each Ba atom is surrounded by seven S atoms that form a distorted mono-capped trigonal prismatic geometry. The polycrystalline Ba4FeCuS6 is semiconducting with a direct bandgap of 1.06(2) eV. The magnetic studies of the sample show an antiferromagnetic transition below 30 K. It will be interesting to explore the photovoltaic properties of Ba4FeCuS6 in the future as it is a direct bandgap semiconductor with Eg ∼ 1 eV.

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来源期刊
New Journal of Chemistry
New Journal of Chemistry 化学-化学综合
CiteScore
5.30
自引率
6.10%
发文量
1832
审稿时长
2 months
期刊介绍: A journal for new directions in chemistry
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