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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Tuning of Electronic Structures of Quasi-One-Dimensional Halogen-Bridged Ni-Pd Mixed-Metal Complexes,[Ni_(1-x)Pd_x(chxn)2X]X2(X = Cl,Br)with Strong Electron Correlation
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Tuning of Electronic Structures of Quasi-One-Dimensional Halogen-Bridged Ni-Pd Mixed-Metal Complexes,[Ni_(1-x)Pd_x(chxn)2X]X2(X = Cl,Br)with Strong Electron Correlation

机译：具有强电子相关性的准一维卤素桥接Ni-Pd混合金属配合物[Ni_（1-x）Pd_x（chxn）2X] X2（X = Cl，Br）的电子结构的调谐

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This article describes the tuning of the electronic structures in a series of quasi-one-dimensional halogen-bridged Ni-Pd mixed-metal complexes,[Ni_(1-x)Pd_x(chxn)2X]X2(chxn = 1R,2R-diaminocyclohexane;X,Y = Cl or Br).In these compounds,planar [M(chxn)2] units are bridged by halogen ions(X),forming linear chain M-X-M structures.Therefore,their electronic structures are 1D and are composed of hybridization between the d_z~2 orbitals of the metal ions and p_z orbitals of the bridging halogens.In this system,electron-correlation on the Ni sites and electron-phonon interaction on the Pd sites should compete with each other.Their electronic structures have been investigated by means of the single-crystal reflectance,ESR and 1R spectroscopies,electrical conductivities,and X-ray diffuse scattering.Moreover,their local electronic structures have been directly observed by scanning tunneling microscopy(STM)using single-crystals at room temperature and under ambient pressure.As a result,while the oxidation state of the Ni sites is +3 in all mixing ratios in these compounds due to strong electron-correlation,the conversion from the Pd~(III)Mott-Hubbard states to the Pd~(II)-Pd~(IV)mixed-valence states is observed around x approx= 0.90 for Br and x approx= 0.85 for CI.Interestingly,the spin-soliton in Ni0.05Pd0.95(chxn)2Br3 was directly observed by STM for the first time.
机译：本文介绍了一系列准一维卤素桥Ni-Pd混合金属配合物[Ni_（1-x）Pd_x（chxn）2X] X2（chxn = 1R，2R-在这些化合物中，平面[M（chxn）2]单元被卤素离子（X）桥接，形成线性链MXM结构。因此，它们的电子结构为一维且由金属离子的d_z〜2轨道与桥连卤素的p_z轨道之间杂化。在该系统中，Ni位上的电子相关性和Pd位上的电子-声子相互作用应相互竞争。通过单晶反射率，ESR和1R光谱，电导率和X射线漫散射进行了研究。此外，在室温下使用单晶通过扫描隧道显微镜（STM）直接观察了它们的局部电子结构。在环境压力下。由于强的电子相关性，这些化合物在所有混合比中Ni位点的氧化态均为+3，从Pd〜（III）Mott-Hubbard态向混合的Pd〜（II）-Pd〜（IV）的转化大约在Br的x约= 0.90和CI的x约= 0.85附近观察到-价态。有趣的是，STM首次直接观察到Ni0.05Pd0.95（chxn）2 Br 3中的自旋孤子。

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