bis(4,4'-dimethyl-2,2'bipyridine)ruthenium(II) oxalate | 244201-39-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: bis(4,4'-dimethyl-2,2'bipyridine)ruthenium(II) oxalate
• CAS: 244201-39-6
• 化学式: C₂O₄*C₂₄H₂₄N₄Ru
• 分子量: 557.571
• InChiKey: UMBJADJVVRDBRE-UHFFFAOYSA-L

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：

  ammonium hexafluorophosphate 、 bis(4,4'-dimethyl-2,2'bipyridine)ruthenium(II) oxalate 、 4,4'-bis(N,N-diethylamino)-2,2'-bipyridine 在 盐酸 作用下， 以 甲醇 为溶剂， 生成 bis(4,4'-dimethyl-2,2'-bipyridine)(4,4'-bis(diethylamino)-2,2'-bipyridine)ruthenium(II) hexafluorophosphate
  参考文献：
  名称：

  Static and Time-Resolved Spectroscopic Studies of Low-Symmetry Ru(II) Polypyridyl Complexes

  摘要：

  The spectroscopic and electrochemical properties of a series of four Ru-II polypyridyl complexes are reported. Compounds of the form [Ru(dmb)(x)(dea)(3-x)](2+) (x = 0-3), where dmb is 4,4'-dimethyl-2,2'-bipyridine and dea is 4,4'-bis (diethylamino)-2,2-bipyridine, have been prepared and studied using static and time-resolved electronic and vibrational spectroscopies as a prelude to femtosecond spectroscopic studies of excited-state dynamics. Static electronic spectra in CH3CN solution reveal a systematic shift of the MLCT absorption envelope from a maximum of 458 nm in the case of [Ru(dmb)(3)](2+) to 518 nm for [Ru(dea)(3)](2+) with successive substitutions of dea for dmb, suggesting a dea-based chromophore as the lowest-energy species. However, analysis of static and time-resolved emission data indicates an energy gap ordering of [Ru(dmb)(3)](2+) > [Ru(dmb)(2)(dea)](2+) > [Ru(dea)312+ > [Ru(dmb)(dea)(2)](2+), at variance with the electronic structures inferred from the absorption spectra. Nanosecond time-resolved electronic absorption and time-resolved step-scan infrared data are used to resolve this apparent conflict and confirm localization of the long-lived (MLCT)-M-3 state on dmb in all three complexes where this;ligand is present, thus making the dea-based excited state unique to [Ru(dea)(3)](2+). Electrochemical studies further reveal the origin of this result, where a strong influence of the dea ligand on the oxidative Ru-II/III couple, due to pi donation from the diethylamino substituent, is observed. The electronic absorption spectra are then reexamined in light of the now well-determined excited-state electronic structure. The results serve to underscore the importance of complete characterization of the electronic structures of transition metal complexes before embarking on ultrafast studies of their excited-state properties.

  DOI：

  10.1021/jp9919415
• 作为产物：
  描述：

  4-Methyl-2-(4-methylpyridin-2-yl)pyridine;ruthenium(2+);chloride 、 草酸 以 水 为溶剂， 以60%的产率得到bis(4,4'-dimethyl-2,2'bipyridine)ruthenium(II) oxalate
  参考文献：
  名称：

  Static and Time-Resolved Spectroscopic Studies of Low-Symmetry Ru(II) Polypyridyl Complexes

  摘要：

  The spectroscopic and electrochemical properties of a series of four Ru-II polypyridyl complexes are reported. Compounds of the form [Ru(dmb)(x)(dea)(3-x)](2+) (x = 0-3), where dmb is 4,4'-dimethyl-2,2'-bipyridine and dea is 4,4'-bis (diethylamino)-2,2-bipyridine, have been prepared and studied using static and time-resolved electronic and vibrational spectroscopies as a prelude to femtosecond spectroscopic studies of excited-state dynamics. Static electronic spectra in CH3CN solution reveal a systematic shift of the MLCT absorption envelope from a maximum of 458 nm in the case of [Ru(dmb)(3)](2+) to 518 nm for [Ru(dea)(3)](2+) with successive substitutions of dea for dmb, suggesting a dea-based chromophore as the lowest-energy species. However, analysis of static and time-resolved emission data indicates an energy gap ordering of [Ru(dmb)(3)](2+) > [Ru(dmb)(2)(dea)](2+) > [Ru(dea)312+ > [Ru(dmb)(dea)(2)](2+), at variance with the electronic structures inferred from the absorption spectra. Nanosecond time-resolved electronic absorption and time-resolved step-scan infrared data are used to resolve this apparent conflict and confirm localization of the long-lived (MLCT)-M-3 state on dmb in all three complexes where this;ligand is present, thus making the dea-based excited state unique to [Ru(dea)(3)](2+). Electrochemical studies further reveal the origin of this result, where a strong influence of the dea ligand on the oxidative Ru-II/III couple, due to pi donation from the diethylamino substituent, is observed. The electronic absorption spectra are then reexamined in light of the now well-determined excited-state electronic structure. The results serve to underscore the importance of complete characterization of the electronic structures of transition metal complexes before embarking on ultrafast studies of their excited-state properties.

  DOI：

  10.1021/jp9919415