1,2-bis(p-N,N-diethylanilinyl)benzene radical cation

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-bis(p-N,N-diethylanilinyl)benzene radical cation
• 英文别名: 4-[2-[4-(diethylamino)phenyl]-3,4,5,6-tetraphenylphenyl]-N,N-diethylaniline
• 化学式: C₅₀H₄₈N₂
• 分子量: 676.945
• InChiKey: AOXHBOHGDYGUIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.4
• 重原子数：
  52
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2-bis(p-N,N-diethylanilinyl)benzene radical cation 、 dodecamethylcarba-closo-dodecaborate 以 二氯甲烷 为溶剂， 以80%的产率得到1,2-bis(p-N,N-diethylanilinyl)tetraphenylbenzene(*+)(dodecamethylcarboranyl(1-)
  参考文献：
  名称：

  Very Fast Electron Migrations within p-Doped Aromatic Cofacial Arrays Leading to Three-Dimensional (Toroidal) π-Delocalization

  摘要：

  The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H-ab) that are required for the evaluation of the activation barrier (Delta G(ET)*) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N, N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range Delta G(ET)* = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T-t > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.

  DOI：

  10.1021/ja060393n
• 作为产物：
  描述：

  1,2-bis(p-N,N-diethylanilinyl)acetylene 生成 1,2-bis(p-N,N-diethylanilinyl)benzene radical cation
  参考文献：
  名称：

  多个芳香中心之间的空间（界面）pi离域化：六苯基苯样自由基阳离子中的环形共轭。

  摘要：

  DOI：

  10.1002/anie.200501005

文献信息

• Through-Space (Cofacial) π-Delocalization among Multiple Aromatic Centers: Toroidal Conjugation in Hexaphenylbenzene-like Radical Cations
  作者：Duoli Sun、Sergiy V. Rosokha、Jay K. Kochi

  DOI：10.1002/anie.200501005

  日期：2005.8.12
• Very Fast Electron Migrations within p-Doped Aromatic Cofacial Arrays Leading to Three-Dimensional (Toroidal) π-Delocalization
  作者：Sergiy V. Rosokha、Ivan S. Neretin、Duoli Sun、Jay K. Kochi

  DOI：10.1021/ja060393n

  日期：2006.7.1

  The charge-resonance phenomenon originally identified by Badger and Brocklehurst lies at the core of the basic understanding of electron movement and delocalization that is possible within p-doped aromatic (face-to-face) arrays. To this end, we now utilize a series of different aryl-donor groups (Ar) around a central platform to precisely evaluate the intramolecular electron movement among these tethered redox centers. As such, the unique charge-resonance (intervalence) absorption bands observed upon the one-electron oxidation or p-doping of various hexaarylbenzenoid arrays (Ar6C6) provide quantitative measures of the reorganization energy (lambda) and the electronic coupling element (H-ab) that are required for the evaluation of the activation barrier (Delta G(ET)*) for electron-transfer self-exchange according to Marcus-Hush theory. The extensive search for viable redox centers is considerably aided by the application of a voltammetric criterion that has led in this study to Ar = N, N-dialkyl-p-anilinyl, in which exceptionally low barriers are shown to lie in the range Delta G(ET)* = 0.3-0.7 kcal mol(-1) for very fast electron hopping or peregrination around the hexagonal circuit among six equivalent Ar sites. Therefore, at transition temperatures T-t > 0.5/R or roughly -20 degrees C, the electron-transfer dynamics become essentially barrierless since the whizzing occurs beyond the continuum of states and effectively achieves complete pi-delocalization.