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

为了分析平面金属络合物在溶液中每个金属原子周围的立体分子结构与其络合物在溶液中的性质有关，我们主要测量了它们的XANES光谱，建立了用DV-Xα分子轨道计算方法进行光谱分析的方法，并阐明了它们的结构与化学性质之间的关系。铜(II)配合物(N，N‘，N“，N’-(2-aminoethyl)-1，4，8，11-tetraazacyclotetradecane))在晶体中形成双核结构。如果Br^-是反阴离子，则该络合物形成桥联结构，如果ClO_4^-是反阴离子，则形成非桥联结构。为了探讨该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^桥联络合物的情况下，两个光谱之间没有变化。然而，在非桥联络合物的情况下，络合物在水溶液…中的XANES光谱更多的离子与晶体中络合物的光谱有明显的差异。两个光谱的DV-Xα计算表明，在水溶液中，络合物是由Br4+或氧原子(ClO4+-中的一个氧原子)形成的桥联结构。双(1，2-二酮)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了两种不同类型的XANES光谱，而它们的吡啶溶液样品只给出了相同的光谱。我们用我们的DV-Xα计算方法利用所提出的模型结构对这些光谱进行了分析，并阐明了它们之间的光谱变化。对于固体样品，在约8340 eV处的光谱变化显示了每个原子之间相互作用的堆积结构的差异，而对于吡啶溶液样品，尽管堆积结构中的相邻分子略有偏离c轴，但络合物给出了唯一的一个结构，即络合物分子一个堆积在另一个之上。这一结果为络合溶液红色的来源提供了很好的信息。[CuBr2(Cyclam)]和[Cu(Cyclam)(H2O)2]F2-4H2O是1，4，8，11-四氮杂环四环戊烷的两种不同类型的配合物，它们在固体和溶液中的XANES谱各不相同。我们用我们的DV-Xα方法对光谱进行了分析，结果表明，不同的谱型是由于水溶液中一个轴向的Br^-与一个H2O分子交换成了Cu(II)，而水溶液中的主要络合物是[CuBr(Cyclam)(H2O)]^+。上述研究表明，用我们的DV-Xα计算方法进行XANES光谱分析是分析固体和溶液中原子间立体相互作用的非常有效的方法。较少

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