[ruthenium(2,2-bipyridine)2(μ-2,3-bis(pyridyl)pyrazine)ruthenium(cyanide)4] | 1374874-03-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [ruthenium(2,2-bipyridine)2(μ-2,3-bis(pyridyl)pyrazine)ruthenium(cyanide)4]
• 英文别名: [Ru(bpy)2(μ-dpp)Ru(CN)4)]
• CAS: 1374874-03-9
• 化学式: C₃₈H₂₆N₁₂Ru₂
• 分子量: 852.845
• InChiKey: ASKIGNDJRQEWSM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [ruthenium(2,2-bipyridine)2(μ-2,3-bis(pyridyl)pyrazine)ruthenium(cyanide)4] 、 硫酸二甲酯 在 NH₄PF₆ 作用下， 以 further solvent(s) 为溶剂， 以71%的产率得到[ruthenium(2,2-bipyridine)2(μ-2,3-bis(pyridyl)pyrazine)ruthenium(methylisocyanide)4](PF6)4
  参考文献：
  名称：

  Ground and excited state dynamics of new dinuclear ruthenium complexes: NMR, UV–Vis, IR, electrochemical, photophysical characterization, and theoretical study of Ru(bpy)2(μ-dpp)Ru(CN–X)4n+ complexes

  摘要：

  Two novel binuclear complexes of ruthenium(II) have been synthesized and characterized by various spectroscopic (NMR, IR, UV-Vis absorption and emission) and electrochemical methods. Extensive and detailed NMR studies of [(bpy)(2)Ru(mu-dpp)Ru(CN)(4)] 1 and [(bpy)(2)Ru(mu-dpp)Ru(CNCH3)(4)](4+) 2 complexes have revealed a dynamic equilibrium between the stereo isomers of the ground-state complexes. Small energy difference between the two isomers of 1 has been estimated using NMR data (2.7 kJ mol(-1)) and by quantum chemistry calculations (4.7 kJ mol(-1)). The relatively broad lowest energy absorption band appearing in the visible range is assigned as overlapping metal-to-ligand charge-transfer (MLCT) d pi(Ru)(A) -> pi*(mu-dpp) (MLCT1A) and d pi(Ru)(B) -> pi*(mu-dpp) (MLCT1B) transitions. The MLCT bands of complex 1 are solvatochromic (e.g. the lowest energy MLCT1 band shifts from 506 to 540 nm upon changing the solvent from water to MeOH), while the same band of the complex 2 is not sensitive to the solvent nature. The luminescence properties of the excited 1 and 2 complexes are significantly different: (i) a rather small blue shift of the emission band (623 cm(-1)) is observed when the luminescence of complex 1 is detected at 77 K in rigid matrix instead of at ambient temperature in liquid phase. This blue shift is considerably larger (1923 cm(-1)) in the case of complex 2. (ii) Time resolved luminescence studies have revealed that the (MLCT1A)-M-3 and (MLCT1B)-M-3 excited states of complex 1 decay independently. On the other hand a dynamic equilibration occurs between two triplet excited states of complex 2. A slight interaction between the metal centers of complex 1 has been assumed by considering the electrochemical data, while a stronger coupling of the ruthenium atoms in complex 2 has been concluded by comparison of the oxidation potentials of the complex 2 with that of other binuclear ruthenium complexes of the metal centers possessing different chemical environment. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.01.024
• 作为产物：
  描述：

  potassium hexacyanoruthenate(II) 、 {Ru(2,2'-bipyridine)2(2,3-bis(pyridyl)pyrazine)}Cl2 在 NH₄PF₆ 、 KOH 作用下， 以 水 为溶剂， 以45%的产率得到[ruthenium(2,2-bipyridine)2(μ-2,3-bis(pyridyl)pyrazine)ruthenium(cyanide)4]
  参考文献：
  名称：

  Ground and excited state dynamics of new dinuclear ruthenium complexes: NMR, UV–Vis, IR, electrochemical, photophysical characterization, and theoretical study of Ru(bpy)2(μ-dpp)Ru(CN–X)4n+ complexes

  摘要：

  Two novel binuclear complexes of ruthenium(II) have been synthesized and characterized by various spectroscopic (NMR, IR, UV-Vis absorption and emission) and electrochemical methods. Extensive and detailed NMR studies of [(bpy)(2)Ru(mu-dpp)Ru(CN)(4)] 1 and [(bpy)(2)Ru(mu-dpp)Ru(CNCH3)(4)](4+) 2 complexes have revealed a dynamic equilibrium between the stereo isomers of the ground-state complexes. Small energy difference between the two isomers of 1 has been estimated using NMR data (2.7 kJ mol(-1)) and by quantum chemistry calculations (4.7 kJ mol(-1)). The relatively broad lowest energy absorption band appearing in the visible range is assigned as overlapping metal-to-ligand charge-transfer (MLCT) d pi(Ru)(A) -> pi*(mu-dpp) (MLCT1A) and d pi(Ru)(B) -> pi*(mu-dpp) (MLCT1B) transitions. The MLCT bands of complex 1 are solvatochromic (e.g. the lowest energy MLCT1 band shifts from 506 to 540 nm upon changing the solvent from water to MeOH), while the same band of the complex 2 is not sensitive to the solvent nature. The luminescence properties of the excited 1 and 2 complexes are significantly different: (i) a rather small blue shift of the emission band (623 cm(-1)) is observed when the luminescence of complex 1 is detected at 77 K in rigid matrix instead of at ambient temperature in liquid phase. This blue shift is considerably larger (1923 cm(-1)) in the case of complex 2. (ii) Time resolved luminescence studies have revealed that the (MLCT1A)-M-3 and (MLCT1B)-M-3 excited states of complex 1 decay independently. On the other hand a dynamic equilibration occurs between two triplet excited states of complex 2. A slight interaction between the metal centers of complex 1 has been assumed by considering the electrochemical data, while a stronger coupling of the ruthenium atoms in complex 2 has been concluded by comparison of the oxidation potentials of the complex 2 with that of other binuclear ruthenium complexes of the metal centers possessing different chemical environment. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.01.024