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Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species
Chemistry of Materials ( IF 7.2 ) Pub Date : 2022-06-07 , DOI: 10.1021/acs.chemmater.2c00270
Colin P. Harmer 1, 2 , Saeed Kamali 3, 4 , Oleg I. Lebedev 5 , Shannon J. Lee 1, 2, 6 , Raquel A. Ribeiro 7 , Paul C. Canfield 2, 7 , Kirill Kovnir 1, 2
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Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe9.4(2)S10][Fe(en)3]0.6(1)·en0.9(3). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe8S10][Fe(en)3]1·en0.5 and tetragonal FeS. The new compound has flat Fe9.4S10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe9.4S10][Fe(en)3]0.6·en0.9, the interlayer space is occupied by [Fe(en)3]2+ complexes and neutral ethylenediamine molecules in a ∼2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (∼6%) of iron vacancies at the Fe-S layer in [Fe9.4S10][Fe(en)3]0.6·en0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure–property relationships.

中文翻译:

层状 FeS 插层中的伪多态性:带电和中性客体之间的竞争

对四面体 FeS-乙二胺插层形成的系统合成研究导致合成了一种新化合物 [Fe 9.4(2) S 10 ][Fe(en) 3 ] 0.6(1) ·en 0.9(3)。基于元素组成、分解行为、高分辨率同步辐射 X 射线衍射和全散射、57 Fe Mössbauer 光谱和电子衍射的协同组合确定了组成和复杂的晶体结构。结构模型是基于与先前报道的结构 [Fe 8 S 10 ][Fe(en) 3 ] 1 ·en的系统比较而得出的0.5和四方 FeS。新化合物具有平坦的 Fe 9.4 S 10层,类似于超导二元 FeS 中的层。在[Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9的晶体结构中,层间空间被[Fe(en) 3 ] 2+占据配合物和中性乙二胺分子的比例约为 2:3。层间物质不是随机取向的,而是有序的,如高分辨率 X 射线衍射和电子衍射图案中的超结构衍射峰所证明的那样。磁性研究表明在 2 K 时没有超导跃迁,表明在 [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 ·en 0.9的 Fe-S 层中存在微量 (~6%) 的铁空位仍然足以移动费米能级的位置,从而导致性质的调整。我们的工作表明了详细表征插层化合物的晶体结构以了解观察到的性质的起源并发展适当的结构-性质关系的重要性。
更新日期:2022-06-07
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