Synthesis of a one-dimensional metal-dimer assembled system with interdimer interaction, M2(dtp)4 (M = Ni, Pd; dtp = dithiopropionato)
Synthesis of a one-dimensional metal-dimer assembled system with interdimer interaction, M2(dtp)4 (M = Ni, Pd; dtp = dithiopropionato)
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DOI：
10.1021/ic051387f
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发表时间：
2006-01-09
影响因子：
4.6
通讯作者：
Kitagawa, H
中科院分区：
文献类型：
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作者：
Kobayashi, A;Kojima, T;Kitagawa, H
合成了金属二聚体组装体系M-2（dtp）（4）（M = Ni，Pd；dtp =二硫代丙酸盐，C2H5CS2-），并通过X射线单晶衍射法、溶液的紫外-可见-近红外光谱、固态漫反射光谱和电导率测量进行了分析。该结构表现出 M-2(dtP)(4) 的一维金属二聚体链，具有适度的二聚体间接触。这些配合物是半导体或绝缘的，这与M-II(d(8))的完全填充的d(Z2)带一致。 Ni-2(dtp)(4) 中二聚体金属间距离为 3.644(2) 埃，Pd-2(dtp)(4) 中二聚体金属间距离为 3.428(2) 埃，每个距离都略长于金属范德华半径的两倍。然而，在漫反射光谱中观察到中间二聚体电荷转移跃迁。这种转变的起源被认为是由于两个相邻 d(a*) 轨道的重叠，由于 M(d(Z2))-M(d(Z2)) 的反键 d(sigma*) 特性，它们比 d(Z2) 轨道展开得更多。 Ni-2(dtp)(4)在相对低的能量区域表现出中间二聚体电荷转移带，这是源自3d(sigma*)的库仑排斥。 Ni 的轨道。
A metal-dimer assembled system, M-2(dtp)(4) (M = Ni, Pd; dtp = dithiopropionate, C2H5CS2-), was synthesized and analyzed by the X-ray single-crystal diffraction method, UV-vis-near-IR spectra of solutions, solid-state diffuse reflectance spectroscopies, and electrical conductivity measurements. The structures exhibit one-dimensional metal-dimer chains of M-2(dtP)(4) with moderate interdimer contact. These complexes are semiconducting or insulating, which is consistent with the fully filled d(Z2) band of M-II(d(8)). Interdimer metal-metal distances were 3.644(2) angstrom in Ni-2(dtp)(4) and 3.428(2) angstrom in Pd-2(dtp)(4), each of which is marginally longer than twice the van der Waals radius of the metal. Interdimer charge-transfer transitions were nevertheless observed in diffuse reflectance spectra. The origin of this transition is considered to be due to an overlap of two adjacent d(a*) orbitals, which spread out more than the d(Z2) orbital because of the antibonding d(sigma*) character of the M(d(Z2))-M(d(Z2)). The Ni-2(dtp)(4) exhibited an interdimer charge-transfer band at a relatively low energy region, which is derived from the Coulomb repulsion of the 3d(sigma*). orbital of Ni.