Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.
Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.
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DOI：
10.1039/c3dt50234a
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发表时间：
2013-04
影响因子：
4
通讯作者：
Xingxun Zhu;Ya‐Ping Ou;Jing Zhang;Jianlong Xia;Jun Yin;Guang‐Ao Yu;Shenghua Liu
中科院分区：
文献类型：
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作者：
Xingxun Zhu;Ya‐Ping Ou;Jing Zhang;Jianlong Xia;Jun Yin;Guang‐Ao Yu;Shenghua Liu
合成了一系列基于二硫杂[3.3]间对环芳的单金属乙炔钌配合物。所有的配合物已充分其特征在于通过NMR光谱，X-射线晶体学和元素分析。同时，测定了它们的紫外/维斯吸收光谱等基本光学性质和电化学性质。(1)H NMR和X-射线晶体结构研究表明，这些钌配合物在溶液和固体状态下均存在分子内C-H···π相互作用。电化学研究表明，二硫杂[3.3]对环芳环上的取代基可以通过分子内C-H···π相互作用影响钌中心的氧化活性.此外，与缺电子基团相比，给电子基团促进钌中心的氧化。研究了某些配合物在中性和氧化态的紫外/维斯吸收光谱和红外光谱。红外光谱研究表明，环蕃上的取代基对配合物中性态的ν（C <$C）谱带有一定的影响，而对氧化态的ν（C <$C）谱带影响不大.
A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.