Spin-Orbit Coupling and Metal-Ligand Interactions in Fe(II), Ru(II), and Os(II) Complexes
Spin-Orbit Coupling and Metal-Ligand Interactions in Fe(II), Ru(II), and Os(II) Complexes
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DOI：
10.1021/jp103884c
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发表时间：
2010-06-10
影响因子：
3.7
通讯作者：
Rensmo, Hakan
中科院分区：
文献类型：
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作者：
Johansson, Erik M. J.;Odelius, Michael;Rensmo, Hakan
实验绘制了M(Bpy)(3)(2+)配合物(bpy=2，2‘-联吡啶，M=Fe(II)，Ru(II)，Os(II))的氧化电位和吸收光谱的能级图。用元素专一性方法，用硬X射线高动能光电子能谱(PES)和X射线吸收光谱(XAS)研究了过渡金属络合物的分子膜。将计算结果与配合物和配体的电子结构计算结果进行了比较。该方法允许我们从实验上测量和解释自旋轨道耦合和金属配体相互作用的能级。具体地说，氧化电位变化趋势的反常可以用Os(Bpy)(3)(2+)的大的自旋轨道耦合来解释。用X射线吸收谱研究了不同金属离子对光吸收形成态的影响，并从光谱中确定了d-sigma和pi贡献产生的能级的相对位置。这些结果解释了Os(Bpy)(3)(2+)的MLCT跃迁能量比Ru(Bpy)(3)(2+)的低。
The purpose of the present paper is to experimentally map the energy levels governing the trends observed in oxidation potentials and absorption spectra of M(bpy)(3)(2+) complexes (bpy = 2,2'-bipyridine, M = Fe(II), Ru(II), and Os(II)). Molecular films of the transition metal complexes were investigated with element specific methods using photoelectron spectroscopy (PES) at high kinetic energy using hard X-rays and by X-ray absorption spectroscopy (XAS). The results were compared to electronic structure calculations on the complexes and the ligand. The approach allows us to experimentally measure and interpret the energy levels in terms of spin orbit coupling and metal ligand interactions. Specifically, it was verified that the anomaly in the trend in oxidation potentials could be explained by a large spin orbit coupling for the Os(bpy)(3)(2+). The influence of the different metal ions on the state formed upon light absorption was also investigated by N Is X-ray absorption, and from the spectra we could determine the relative position of the levels originating from d-sigma and pi contributions. The results for the occupied and unoccupied electronic levels explain the lower energy of the MLCT transition of the Os(bpy)(3)(2+) in comparison to the Ru(bpy)(3)(2+).