Cs8[Fe4S10] and Cs7[Fe4S8], two new sulfido ferrates with different tetrameric anions.
Cs8[Fe4S10] and Cs7[Fe4S8], two new sulfido ferrates with different tetrameric anions.
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Cs8[Fe4S10] 和 Cs7[Fe4S8]，两种具有不同四聚阴离子的新型硫代高铁酸盐
DOI：
10.1021/ic502382v
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发表时间：
2015
影响因子：
4.6
通讯作者：
C. Röhr
中科院分区：
文献类型：
--
作者：
M. Schwarz;C. Röhr
从含有元素Fe和S的化学计量比样品中合成了两种新的硫化铯铁酸盐Cs8[Fe4S10]和Cs7[Fe4S8]，最高温度为1070K。用单晶X射线衍射法测定了它们的晶体结构。Cs8[FeIII4S10]为三斜晶型CS6[Ga4Se10]结构，与相应的Ru盐同型。该结构表现出边共享四面体的四聚体[Fe4S10]8-，它代表了众所周知的链状化合物A[FeS2]的片段。单斜混价铁(II/III)硫化高铁酸盐Cs7[Fe4S8]与碲化铯高铁酸铯是同型的，同样含有四个边共享的[FeS4]四面体的低聚四聚体，在这种情况下只产生轻微扭曲的四面体[Fe4S8]7-阴离子，其Fe4S4立方烷核类似于突出的[Fe4(μ3-S4)]+簇，例如在铁氧还蛋白的活性中心。这些硫化高铁酸盐阴离子被26个Cs阳离子包围，这些阳离子位于立方体的8个角、6个面和12个边。这些立方体的密集堆积最终导致每个团簇阴离子总共有七个铯反离子，这完全描述了整体晶体结构。根据这种以团簇为中心的立方排列，应用结晶学基团-亚基形式，可以建立Cs离子和团簇阴离子的堆积与简单的立方堆积(α-Po结构)的关系。利用两个四聚体中高自旋Fe离子的反铁磁自旋有序的FP-LAPW能带结构计算，预测了Cs8[FeI4S10]的L→M-CT的小禁带宽度为1 eV，混价团簇化合物Cs7[FeI4S8]的d-d跃迁产生的小带隙为0.1eV。
The two new cesium sulfido ferrates Cs8[Fe4S10] and Cs7[Fe4S8] were synthesized at a maximum temperature of 1070 K in corundum crucibles from stoichiometric samples containing elemental Fe and S together with cesium disulfide, Cs2S2. Their crystal structures have been determined by means of single-crystal X-ray diffraction. Cs8[FeIII4S10] crystallizes in the triclinic Cs6[Ga4Se10]-type structure and is thus isotypic to the corresponding rubidium salt. The structure exhibits tetramers [Fe4S10]8–of edge-sharing tetrahedra, which represent segments of the well-known chain compounds A[FeS2]. The monoclinic mixed-valent iron(II/III) sulfido ferrate Cs7[Fe4S8], which is isotypic to the cesium tellurido ferrate, likewise contains oligomeric tetramers of four edge-sharing [FeS4] tetrahedra, in this case resulting in only slightly distorted tetrahedral [Fe4S8]7–anions with a Fe4S4cubane core resembling the prominent [Fe4(μ3-S4)]+cluster, e.g., in the active site of ferredoxins. These sulfido ferrate anions are surrounded by 26 Cs cations, which are located at the 8 corners, 6 faces, and 12 edges of a cube. A dense stacking of these cubes, which ultimately results in the overall seven cesium countercations per cluster anion, describes the overall crystal structure completely. According to this arrangement of cluster-centered cubes, a relationship of the packing of Cs cations and cluster anions with the simple cubic packing (α-Po-type structure) can be established by applying the crystallographic group–subgroup formalism. FP-LAPW band-structure calculations applying antiferromagnetic spin ordering of the high-spin Fe ions in the two tetramers predict a small band gap of 1 eV associated with a L → M-CT for Cs8[FeIII4S10] and a tiny energy gap of 0.1 eV resulting from a d–d transition for the mixed-valent cluster compound Cs7[FeII/III4S8].
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DOI：
10.1002/zaac.201400357
发表时间：
2014-11
期刊：
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