4,4'-di(phenylethynylbenzene)-2,2'-bipyridine | 438450-77-2

• 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: 4,4'-di(phenylethynylbenzene)-2,2'-bipyridine
• 英文别名: 4-[2-(4-Phenylphenyl)ethynyl]-2-[4-[2-(4-phenylphenyl)ethynyl]pyridin-2-yl]pyridine；4-[2-(4-phenylphenyl)ethynyl]-2-[4-[2-(4-phenylphenyl)ethynyl]pyridin-2-yl]pyridine
• CAS: 438450-77-2
• 化学式: C₃₈H₂₄N₂
• 分子量: 508.622
• InChiKey: RJLFUCJQXNWLJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 4,4'-di(phenylethynylbenzene)-2,2'-bipyridine 以 甲苯 为溶剂， 以79%的产率得到fac-[(4,4'-di(phenylethynylbenzene)-2,2'-bipyridine)Re(CO)3Cl]
  参考文献：
  名称：

  Experimental Studies of Light-Induced Charge Transfer and Charge Redistribution in (X₂-Bipyridine)Re^I(CO)₃Cl Complexes

  摘要：

  Stark emission spectroscopy, transient DC photoconductivity (TDCP), and ground-state dipole moment measurements have been used to evaluate charge transfer (CT) within various (X-2-bipyridine)Re-I(CO)(3)Cl complexes following (MLCT)-M-3 excited-state formation. The Stark technique reports on vector differences between ground-state (mu(g)) and excited-state (mu(e)) dipole moments, while TDCP, when combined with independently obtained mu(g) information, reports on scalar differences, For systems featuring collinear, same-signed ground- and excited-state dipole moments, the scalar and vector differences are equivalent. However, for the low symmetry systems studied here, they are distinctly different. The vector difference yields the effective adiabatic one-electron-transfer distance (R-12), while the combined vector and scalar data yield information about dipole rotation upon ground-state/excited-state interconversion. For the systems examined, charge transfer distances are substantially smaller than geometric electron-donor/electron-acceptor site separation distances, The measured distances are significantly affected by changes in acceptor ligand substituent composition. Electron-donating substituents decrease CT distances, while electron-withdrawing substituents increase CT distances, as do aromatic substituents that are capable of expanding the bipyridyl ligand (acceptor ligand) pi system. The Stark measurements additionally indicate that the CT vector and the transition dipole moment are significantly orthogonal, a consequence of strong polarization of the Re-Cl bond (orthogonal to the metal/acceptor-ligand plane) in the ground electronic state and relaxation of the polarization in the upper state. The ground-state Re-Cl bond polarization is sufficiently large that the overall ground-state scalar dipole moment exceeds the overall excited-state scalar dipole moment, despite transfer of an electron from the metal center to the diimine ligand. This finding provides an explanation for the otherwise puzzling negative solvatochromism exhibited in this family of compounds. Combining TDCP and Stark results, we find that the dipole moment can be rotated in some instances by more than 90degrees upon (MLCT)-M-3 excited-state formation. The degree of rotation or reorientation can be modulated by changing the identity of the acceptor ligand substituents. Reorientational effects are smallest when the compounds feature aromatic substituents capable of spatially extending the pi system of the acceptor ligand.

  DOI：

  10.1021/ic011015g

文献信息

• Experimental Studies of Light-Induced Charge Transfer and Charge Redistribution in (X₂-Bipyridine)Re^I(CO)₃Cl Complexes
  作者：Keith A. Walters、Young-Jin Kim、Joseph T. Hupp

  DOI：10.1021/ic011015g

  日期：2002.6.1

  Stark emission spectroscopy, transient DC photoconductivity (TDCP), and ground-state dipole moment measurements have been used to evaluate charge transfer (CT) within various (X-2-bipyridine)Re-I(CO)(3)Cl complexes following (MLCT)-M-3 excited-state formation. The Stark technique reports on vector differences between ground-state (mu(g)) and excited-state (mu(e)) dipole moments, while TDCP, when combined with independently obtained mu(g) information, reports on scalar differences, For systems featuring collinear, same-signed ground- and excited-state dipole moments, the scalar and vector differences are equivalent. However, for the low symmetry systems studied here, they are distinctly different. The vector difference yields the effective adiabatic one-electron-transfer distance (R-12), while the combined vector and scalar data yield information about dipole rotation upon ground-state/excited-state interconversion. For the systems examined, charge transfer distances are substantially smaller than geometric electron-donor/electron-acceptor site separation distances, The measured distances are significantly affected by changes in acceptor ligand substituent composition. Electron-donating substituents decrease CT distances, while electron-withdrawing substituents increase CT distances, as do aromatic substituents that are capable of expanding the bipyridyl ligand (acceptor ligand) pi system. The Stark measurements additionally indicate that the CT vector and the transition dipole moment are significantly orthogonal, a consequence of strong polarization of the Re-Cl bond (orthogonal to the metal/acceptor-ligand plane) in the ground electronic state and relaxation of the polarization in the upper state. The ground-state Re-Cl bond polarization is sufficiently large that the overall ground-state scalar dipole moment exceeds the overall excited-state scalar dipole moment, despite transfer of an electron from the metal center to the diimine ligand. This finding provides an explanation for the otherwise puzzling negative solvatochromism exhibited in this family of compounds. Combining TDCP and Stark results, we find that the dipole moment can be rotated in some instances by more than 90degrees upon (MLCT)-M-3 excited-state formation. The degree of rotation or reorientation can be modulated by changing the identity of the acceptor ligand substituents. Reorientational effects are smallest when the compounds feature aromatic substituents capable of spatially extending the pi system of the acceptor ligand.