Electronic Structure and Circular Dichroism of Tris(bipyridyl) Metal Complexes within Density Functional Theory
Electronic Structure and Circular Dichroism of Tris(bipyridyl) Metal Complexes within Density Functional Theory
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DOI：
10.1021/ic9011586
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发表时间：
2010-02-15
影响因子：
4.6
通讯作者：
Ziegler, Tom
中科院分区：
文献类型：
--
作者：
Fan, Jing;Autschbach, Jochen;Ziegler, Tom
用含时密度泛函理论（TD-DFT）计算了三双齿铁基配合物[M（L-L）（3）]（2+）（M = Fe，Ru，Os; L-L = 2，2 '-bipyridine）的电子圆二色谱（CD）.模拟的CD光谱与实验进行了比较，并得到了相当好的协议。在这项研究中，已经作出了很大的努力来解释激子CD所产生的长轴极化的π-> π * 激发的配合物的配体。金属-配体轨道相互作用以及激子跃迁的光学活性的起源已阐明与TD-DFT结果的详细分析中的一般模型，适用于类似的手性化合物。
Time-dependent density functional theory (TD-DFT) has been employed to calculate the electronic circular dichroism (CD) spectra of tris-bidentate iron group complexes [M(L-L)(3)](2+) (M = Fe, Ru, Os; L-L = 2,2'-bipyridine). The simulated CD spectra are compared with the experiment, and reasonably good agreement is obtained, In this study, much effort has been made to interpret the exciton CD arising from the long-axis-polarized pi -> pi* excitations in the ligands of the complexes. Metal-ligand orbital interactions as well as the origin of the optical activity of the exciton transitions have been elucidated in connection with the detailed analysis of the TD-DFT results within a general model that is applicable to similar chiral compounds.