cis,cis-[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(CO)2(CF3SO3)2] | 169832-44-4

• 英文名称: cis,cis-[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(CO)2(CF3SO3)2]
• 英文别名: [Ru(diethyl 2,2'-bipyridine-4,4'-dicarboxylate)(CO)2(CF3SO2)2]
• CAS: 169832-44-4
• 化学式: C₂₀H₁₆F₆N₂O₁₂RuS₂
• 分子量: 755.546
• InChiKey: OZYALHNXBBAQIJ-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 、 2,2'-联吡嗪 、 cis,cis-[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(CO)2(CF3SO3)2] 以 乙醇 为溶剂， 以45%的产率得到[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(2,2'-bipyrazine)(CO)2](PF6)2
  参考文献：
  名称：

  Designed Synthesis of Mononuclear Tris(heteroleptic) Ruthenium Complexes Containing Bidentate Polypyridyl Ligands

  摘要：

  A general synthetic methodology is reported for tris(bidentate)ruthenium(II) complexes containing three different polypyridyl ligands, based on the sequential addition of the ligands to the oligomer [Ru(CO)(2)Cl-2](n). The tris(heteroleptic) complexes were characterized by FAB mass spectrometry and NMR spectroscopy. An X-ray crystal structure determination was made for the complex, [Ru(Me(2)bpy)(phen)(bpa)](PF6)(2) . C6H14 [C40H43F12N7P2Ru, M = 1062.8; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine, phen = 1,10-phenanthroline, bpa = bis(2-pyridyl)amine]: triclinic, space group , a = 14.57(3) Angstrom, b = 13.50(3) Angstrom, c = 12.73(3) Angstrom, alpha = 68.6(2)degrees, beta = 63.5(1)degrees, gamma = 79.8(2)degrees, V = 2082 Angstrom(3), Z = 2. Aspects of the electrochemistry, spectroscopy, and photophysics of the tris(heteroleptic) species are discussed.

  DOI：

  10.1021/ic00128a028
• 作为产物：
  描述：

  trans(Cl)-[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(CO)2Cl2] 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以26%的产率得到cis,cis-[Ru(4,4'-bis(carboxyethyl)-2,2'-bipyridine)(CO)2(CF3SO3)2]
  参考文献：
  名称：

  Designed Synthesis of Mononuclear Tris(heteroleptic) Ruthenium Complexes Containing Bidentate Polypyridyl Ligands

  摘要：

  A general synthetic methodology is reported for tris(bidentate)ruthenium(II) complexes containing three different polypyridyl ligands, based on the sequential addition of the ligands to the oligomer [Ru(CO)(2)Cl-2](n). The tris(heteroleptic) complexes were characterized by FAB mass spectrometry and NMR spectroscopy. An X-ray crystal structure determination was made for the complex, [Ru(Me(2)bpy)(phen)(bpa)](PF6)(2) . C6H14 [C40H43F12N7P2Ru, M = 1062.8; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine, phen = 1,10-phenanthroline, bpa = bis(2-pyridyl)amine]: triclinic, space group , a = 14.57(3) Angstrom, b = 13.50(3) Angstrom, c = 12.73(3) Angstrom, alpha = 68.6(2)degrees, beta = 63.5(1)degrees, gamma = 79.8(2)degrees, V = 2082 Angstrom(3), Z = 2. Aspects of the electrochemistry, spectroscopy, and photophysics of the tris(heteroleptic) species are discussed.

  DOI：

  10.1021/ic00128a028

文献信息

• Manipulating the properties of MLCT excited states
  作者：Peter A. Anderson、F. Richard Keene、Thomas J. Meyer、John A. Moss、Geoffrey F. Strouse、Joseph A. Treadway

  DOI：10.1039/b206375a

  日期：——

  Systematic variation of the ligand environment has allowed design of the absorbance characteristics of polypyridyl complexes of ruthenium(II) to produce “black absorbers” which absorb throughout the visible region. The presence of acceptor ligands with low-lying π* levels red shift the energies of the lowest energy MLCT bands, while MLCT and π → π* bands originating on other ligands can be used to fill in the higher-energy regions of the spectrum. Incorporation of anionic ligands or other electron-donating ligands causes a red shift in MLCT band energies compared to bpy by manipulation of dπ energy levels. Attention to these design principles has led to the synthesis of complexes which absorb appreciably in the near IR, and are free from complications caused by thermally accessible dd states. Although their emission energies (and energy gaps) are at low energy in the near IR, the use of lowest lying, delocalised acceptor ligands provides lifetime enhancements (compared to bpy) that can be dramatic.

  配体环境的系统性变化使得设计钌（II）的多吡啶络合物的吸收特性成为可能，从而制造出在整个可见光区域都能吸收的 "黑色吸收体"。具有低位 π* 水平的受体配体的存在会使最低能量的 MLCT 带的能量发生红移，而源自其他配体的 MLCT 和 π → π* 带则可用于填充光谱的高能区域。通过操纵 dπ 能级，掺入阴离子配体或其他电子捐赠配体会导致 MLCT 带能发生红移。根据这些设计原则，我们合成出了在近红外波段有明显吸收的配合物，而且这些配合物不会因热可及的 dd 态而引起复杂问题。虽然它们的发射能（和能隙）在近红外处于低能状态，但使用最低位的非定位受体配体可以显著提高寿命（与铋相比）。