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设计合成了3个含不同取代基的二硫杂[3.3]对环番单金属钌炔基化合物6b~6d及一个对照化合物6a.4个化合物通过1H NMR,13C NMR,31P NMR和元素分析进行了表征.化合物6c的结构通过X射线单晶衍射证实,晶体结构显示环芳中上下苯环间存在明显的?–?作用.同时还利用电化学、红外光谱以及密度泛函理论计算,探究了二硫杂[3.3]对环番配体及其上取代基对金属钌中心电子性质的影响.电化学研究结果显示,二硫杂[3.3]对环番上取代基(F,CN)可以通过分子内的跨环?–?作用影响钌中心的氧化还原活性,其中氰基的影响最大.密度泛函理论计算结果显示取代基(F,CN)对配合物的最低未占分子轨道(LUMO)电子云密度分布影响较大,氰基取代的6c和氟取代的6d,其LUMO轨道上的电子几乎定域在桥配体的环番上,而6a和6b,其LUMO轨道上的电子几乎定域在金属钌及其辅配体上.
Three compounds with different substituents of dithia [3.3] dichlorobenzenesulfonyl chloride 6b ~ 6d and one control compound 6a were designed and synthesized.4H NMR, 13C NMR, 31P NMR and elemental analysis The structure of compound 6c was confirmed by X-ray single crystal diffraction and the crystal structure showed that there was a pronounced? -? Interaction between the upper and lower benzene rings in the ring. Meanwhile, electrochemical, infrared spectroscopy and density functional theory The effect of dithia- [3.3] on the electronic properties of ring-like ligands and their substituents on the center of ruthenium metal.The results of electrochemical studies showed that the dithia [3.3] The cross-ring? -? Effect in the molecule affects the redox activity of the ruthenium center, of which the cyano group has the greatest effect. The density functional theory calculations show that the lowest unoccupied molecular orbital (LUMO) The electron cloud density distribution has a great influence on the LUMO orbitals, and the electrons on the LUMO orbitals are almost localized on the ring of the bridged ligands, while the electrons on the LUMO orbitals are nearly constant at 6a and 6b The domain is on the metal ruthenium and its co-ligands.