Stereo molecular structures around each metal atom of planar metal complexes in solution analyzed by the combination of some instrumental analyses

为了分析平面金属配合物在溶液中各金属原子周围的立体分子结构，并与配合物在溶液中的性质相联系，我们主要测量了它们的XANES光谱，建立了用DV-Xα分子轨道计算的光谱分析方法，阐明了它们的结构与化学性质之间的关系。（N，N '，N”，N“'-四（2-氨乙基）-1，4，8，11-四氮杂环十四烷）铜（Ⅱ）配合物在晶体中形成双核结构。当Br^-为抗衡阴离子时，该配合物形成桥连结构;当ClO_4^-为抗衡阴离子时，该配合物形成非桥连结构。为了探讨配合物在溶液中的行为，我们测量了该配合物在晶体和水溶液中的XANES光谱，并用DV-Xα方法进行了分析。在Br^-桥连络合物的情况下，两个光谱之间没有变化。而对于非桥连的配合物，其水溶液的XANES谱图则不一致， ...更多信息 离子的光谱与晶体中配合物的光谱有明显的差异。DV-Xα计算结果表明，配合物在水溶液中形成Br^-或氧原子（ClO_4^-阴离子中有一个氧原子）桥联结构。双（1，2-dione diozimato）镍（II）配合物形成两种不同类型的一维堆积结构。配合物的晶体样品给出两种不同类型的XANES谱，而它们的吡啶溶液样品给出相同的XANES谱。我们使用我们的DV-Xα计算方法分析了这些光谱，并澄清了它们之间的光谱变化。在固体样品的情况下，在约8340 eV处的光谱变化显示了它们的堆叠结构中每个原子相互作用之间的差异，并且在吡啶溶液样品的情况下，络合物给出了唯一一种结构，其中络合物分子一个堆叠在另一个之上，尽管堆叠结构中的相邻分子略微偏离c轴。结果为络合物溶液红色的来源提供了较好的信息。[CuBr[Cu（cyclam）（H_2O）_2]F_2·4H_2O是cyclam与1，4，8，11-四氮杂环十四烷的两种不同类型的配合物，它们在固溶状态下的XANES谱也不同。用DV-Xα方法对光谱进行了分析，结果表明，在水溶液中，Cu（II）与Br^-离子发生了轴向交换，形成了不同的光谱模式，主要络合物为[CuBr（cyclam）（H_2O）]^+。上述研究表明，采用DV-Xα计算方法的XANES光谱分析是分析固体和溶液中立体原子间相互作用的一种非常有效的方法。少

To analyze stereo molecular structures around each metal atom of planar metal complexes in solution which are related to the character of their complexes in solution, we mainly have measured XANES spectra of them, established the spectral analysis method using a DV-Xα molecular orbital calculation method, and clarified the relationship between their structures and chemical characters. The copper (II) complex of (N,N', N", N'''-tetrakis (2-aminoethyl)-1,4,8,11-tetraazacyclotetradecane) forms a dinuclear structure in crystal. If Br^- is a counter anion this complex forms a bridged structure, and forms an unbridged one if ClO_4^- is a counter anion. To discuss the behavior of the complex in solution, we measured XANES spectra of this complex in crystal and in aqueous solution and analyzed the spectra with a DV-Xα method. In case of the Br^- bridged complex, there is no change between both spectra. However, in case of the unbridged complex, the XANES spectra of the complex in aqueous solut … More ion show the clear difference with the spectra of the complex in crystal. The DV-Xα calculation for both spectra clarified that the complexes in aqueous solution form a bridged structure by Br^- or oxygen atom (one oxygen atom in ClO_4^- anion). Bis (1,2-dione diozimato) nickel (II) complexes form two different types of one dimensional stacking structures. The crystal samples of the complexes give two different type XANES spectra, however, the pyridine solution samples of them give only the same spectra. We analyzed those spectra by our DV-Xα calculation method using proposed model structures, and clarified the spectral change, between them. In case of solid samples the spectral change at about 8340eV shows the difference between each atomic interaction in their stacking structures, and in case of pyridine solution samples the complexes give the only one structure which the complex molecules are stacked one above the other, although adjacent molecules in the stacking structures slightly deviate from the c axis. The result gives good information for the origin of red color of the complex solution. [CuBr_2(cyclam)] and [Cu(cyclam)(H_2O)_2]F_2-4H_2O are two different type complexes of cyclam, 1,4,8,11-tetraaza cyclotetradencane, and the XANES spectra of these complexes in solid and solution are different with each other. We analyzed the spectra using our DV-Xα method, and the results suggest that the different spectral patterns are caused by exchanging one axial Br^- with an H_2O molecule to Cu(II) in aqueous solution and the predominant complex in aqueous solution is [CuBr(cyclam)(H_2O)]^+. The upper mentioned studies show XANES spectral analysis by our DV-Xα calculation method is very effective method for analyzing stereoscopic inter-atomic interactions in solid and in solution. Less