论文部分内容阅读
用ＣＮＤＯ／２方法经ＳＣＦ计算获得了钌（Ⅱ）联吡啶配合物ｃｉｓ－［ＲｕⅡ（ｂｐｙ）２（Ｌ）２］的电子结构（其中ｂｐｙ＝２，２′－二联吡啶；Ｌ＝Ｃｌ－，ＮＣＳ－，ＣＮ－，ＮＨ３，ＮＣＣＨ３）．计算结果表明，这些钌（Ⅱ）联吡啶配合物的ＬＵＭＯ均定域于配体ｂｐｙ的最低能π轨道，而其ＨＯＭＯ均定域于中心钌（Ⅱ）原子的ｄπ轨道．随着配体Ｌ的σ电子给予能力的增强，对应配合物的ＨＯＭＯ能级相应增大，ＬＵＭＯ能级亦有所增大，两者之差值则降低．这些钌（Ⅱ）联吡啶配合物的ＨＯＭＯ和ＬＵＭＯ能级变化趋势分别与相应的第一氧化和第一还原电势变化趋势相同，并且ＨＯＭＯ和ＬＵＭＯ能级与其光谱最低吸收能和第一氧化还原电势呈现出很好的线性相关性．计算结果与实验数据相吻合．
The electronic structure of cis- [RuⅡ (bpy) 2 (L) 2] (where bpy = 2,2’-bipyridine; L = Cl -, NCS-, CN-, NH3, NCCH3). The calculated results show that the LUMOs of these ruthenium (Ⅱ) bipyridyl complexes are all localized to the lowest π orbital of the ligand bpy, while the HOMOs are localized to the dπ orbital of the central ruthenium (Ⅱ) atom. With the enhancement of the σ electron donating ability of the ligand L, the HOMO energy levels of the corresponding complexes increase correspondingly, and the levels of LUMO also increase, and the difference between the two decreases. The trends of the HOMO and LUMO energy levels of these ruthenium (II) bipyridyl complexes are the same as that of the corresponding first oxidation and first reduction potential, respectively, and the HOMO and LUMO energy levels are related to their lowest absorption spectra and the first redox potential Showing a good linear correlation. The calculated results are consistent with the experimental data.