Baranov A I, Kloo L, Olenev A V, Popovkin B A, Romanenko A I
Department of Materials Science, Moscow State University, Vorob'evy Gory, Moscow, 119992, Russia.
Inorg Chem. 2003 Jun 30;42(13):3988-93. doi: 10.1021/ic0340332.
The new compound Ni(8)Bi(8)SI(2) has been synthesized and its crystal structure determined by X-ray crystallography. The structure contains one-dimensional (1D) cations (1)( infinity )Ni(8)Bi(8)S separated by iodine anions. The geometry of the columns is similar to that of the recently reported (1)( infinity )Ni(8)Bi(8)S, and the main difference between them is only their formal charge. Electronic structure calculations and physical properties measurements were performed to analyze the influence of the number of valence electrons on the bonding and properties of compounds containing these 1D cations. It was shown that the removal of one electron (i.e., (1)( infinity )Ni(8)Bi(8)S --> (1)( infinity )Ni(8)Bi(8)S) mainly affects the Ni-S bonding within the cation and essentially has no influence on the intermetallic Ni-Bi bonding. It was found that Ni(8)Bi(8)SI(2) containing double-charged columns has conductivity properties more similar to a pure 1D metal than the congener Ni(8)Bi(8)SI containing mono-charged columns.
新化合物Ni(8)Bi(8)SI(2)已被合成，其晶体结构通过X射线晶体学确定。该结构包含由碘阴离子分隔的一维(1D)阳离子(1)(∞)Ni(8)Bi(8)S。这些柱的几何形状与最近报道的(1)(∞)Ni(8)Bi(8)S相似，它们之间的主要区别仅在于其形式电荷。进行了电子结构计算和物理性质测量，以分析价电子数对含有这些一维阳离子的化合物的键合和性质的影响。结果表明，去除一个电子（即(1)(∞)Ni(8)Bi(8)S→(1)(∞)Ni(8)Bi(8)S）主要影响阳离子内的Ni-S键合，而对金属间Ni-Bi键合基本没有影响。发现含有双电荷柱的Ni(8)Bi(8)SI(2)比含有单电荷柱的同系物Ni(8)Bi(8)SI具有更类似于纯一维金属的导电性能。
