Metastable Bi8Ni8S by Reductive Pseudomorphosis of Bi8Ni8SI2
Metastable Bi8Ni8S by Reductive Pseudomorphosis of Bi8Ni8SI2
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通过 Bi8Ni8SI2 的还原假晶实现亚稳态 Bi8Ni8S
DOI：
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发表时间：
2011
期刊：
影响因子：
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通讯作者：
M. Ruck
中科院分区：
文献类型：
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作者：
Martin Kaiser;A. Isaeva;R. Skrotzki;U. Schwarz;M. Ruck
用n-BuLi还原Bi8Ni8SI2，合成了双金属亚硫化物Bi8Ni8S。Bi8Ni8S是亚稳态的，在180℃左右放热分解。在假形态中，前驱体的黑色晶体被保留，而碘离子被提取，预形成的[Bi8Ni8S]碎片重新排列成伪六边形棒状填料[空间群pam， a = 1750.14(7) pm, b = 1007.7(2) pm, c = 419.6(3) pm]。该棒的有效直径约为1nm，由铋原子的外八角形管和镍原子的内八角形管组成。这种排列明显类似于柱状的Ta4Te4Si结构类型。不同之处在于位于中轴上的二硫化物基团。棒内部的原子间距离几乎不受还原的影响，因此电子能带结构没有太大改变。然而，额外的电子将费米能级提高到态密度的局部最大值，并主要占据反键Ni-Ni和S-S态。主要的Bi-Ni多中心键伴随着镍原子间的定域双中心键。镍原子的电荷以及Ni-Ni和Ni-Bi键的ELI-D盆地居群发生了很大的变化，表明该电子管具有相当灵活的（非）充电功能，可以作为电子储存库。与碘化物前体相比，Bi8Ni8S的弱泡利顺磁性略有增强，并且在20 K以下观察到自旋相关。
The bimetallic subsulfide Bi8Ni8S was synthesized by reduction of Bi8Ni8SI2 with n-BuLi. Bi8Ni8S is metastable and decomposes exothermically at about 180 °C. In a pseudomorphosis, the shiny black crystals of the precursor were preserved, while the iodide ions were extracted and the pre-formed [Bi8Ni8S] fragments rearranged into a pseudo-hexagonal rod packing [space group Pbam, a = 1750.14(7) pm, b = 1007.7(2) pm, c = 419.6(3) pm]. The rods have an effective diameter of about 1 nm and consist of an outer octagonal tube of bismuth atoms and an inner octagonal tube of nickel atoms. This arrangement markedly resembles the columnar Ta4Te4Si structure type. The difference comes with the disulfide groups that reside on the central axis. Interatomic distances inside the rods are almost not affected by the reduction, and thus the electronic band structure is not much altered. Yet, the additional electrons raise the Fermi level into a local maximum of the density of states and occupy predominantly antibonding Ni–Ni and S–S states. The dominant Bi–Ni multicenter bonding is accompanied by localized two-center bonds between nickel atoms. The charges of the nickel atoms as well as ELI-D basin populations of Ni–Ni and Ni–Bi bonds change considerably, indicating that the tube is (un)charging quite flexibly and acts as an electron reservoir. In contrast to the iodide precursor, the weak Pauli paramagnetism of Bi8Ni8S is slightly enhanced and spin correlations are observed below 20 K.
影响因子：
21.8
作者：
通讯作者：
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