[3-[4-(dimethylamino)phenyl]buta-1,3-diene-1,1,4,4-tetracarbonitrile-2-yl]corannulene | 1414381-59-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: [3-[4-(dimethylamino)phenyl]buta-1,3-diene-1,1,4,4-tetracarbonitrile-2-yl]corannulene
• 英文别名: 2-[4-(Dimethylamino)phenyl]-3-(2-hexacyclo[11.5.2.04,17.07,16.010,15.014,18]icosa-1,3,5,7(16),8,10(15),11,13,17,19-decaenyl)buta-1,3-diene-1,1,4,4-tetracarbonitrile；2-[4-(dimethylamino)phenyl]-3-(2-hexacyclo[11.5.2.04,17.07,16.010,15.014,18]icosa-1,3,5,7(16),8,10(15),11,13,17,19-decaenyl)buta-1,3-diene-1,1,4,4-tetracarbonitrile
• CAS: 1414381-59-1
• 化学式: C₃₆H₁₉N₅
• 分子量: 521.58
• InChiKey: IPTOENJWROOGSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  41
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  98.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  monobromocorannulene 在 哌啶 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三苯基膦 作用下， 以 1,1,2,2-四氯乙烷 为溶剂， 反应 25.0h， 生成 [3-[4-(dimethylamino)phenyl]buta-1,3-diene-1,1,4,4-tetracarbonitrile-2-yl]corannulene
  参考文献：
  名称：

  Structural, Optical, and Electrochemical Properties of Three-Dimensional Push–Pull Corannulenes

  摘要：

  Electrochemically active corannulene derivatives with various numbers of electron-donating 4-(N,N-dimethylamino)phenylethynyl (1-4) or electron-withdrawing cyanobutadienyl peripheral substitutents (5-8) were prepared. The latter derivatives resulted from formal [2 + 2] cycloaddition of cyanoolefins to 1-4 followed by retro-electrocyclization. Conformational properties were examined by variable-temperature NMR and X-ray diffraction and opto-electronic properties by electronic absorption/emission spectra and electrochemical measurements; these analyses were corroborated by dispersion-corrected density functional calculations at the level of B97-D/def2-TZVPP. In CH2Cl2, 1-4 exhibit intramolecular charge-transfer (ICT) absorptions at 350-550 nm and green (lambda(em) similar to 540 nm) or orange (600 nm) fluorescence with high quantum yields (56-98%) and are more readily reduced than corannulene by up to 490 mV. The variation of optical gap and redox potentials of 1-4 does not correlate with the number of substituents. Cyanobutadienyl corannulenes 5-8 show red-shifted ICT absorptions with end-absorptions approaching 800 nm. Intersubstituent interactions lead to distortions of the corannulene core and lower the molecular symmetry. NMR, X-ray, and computational studies on 5 and 8 with one cyanobutadienyl substituent suggested the formation of intermolecular corannulene dimers. Bowl-inversion barriers around Delta G(double dagger) = 10-11 kcal/mol were determined for these two molecules.

  DOI：

  10.1021/jo302217n

文献信息

• Structural, Optical, and Electrochemical Properties of Three-Dimensional Push–Pull Corannulenes
  作者：Yi-Lin Wu、Mihaiela C. Stuparu、Corinne Boudon、Jean-Paul Gisselbrecht、W. Bernd Schweizer、Kim K. Baldridge、Jay S. Siegel、François Diederich

  DOI：10.1021/jo302217n

  日期：2012.12.21

  Electrochemically active corannulene derivatives with various numbers of electron-donating 4-(N,N-dimethylamino)phenylethynyl (1-4) or electron-withdrawing cyanobutadienyl peripheral substitutents (5-8) were prepared. The latter derivatives resulted from formal [2 + 2] cycloaddition of cyanoolefins to 1-4 followed by retro-electrocyclization. Conformational properties were examined by variable-temperature NMR and X-ray diffraction and opto-electronic properties by electronic absorption/emission spectra and electrochemical measurements; these analyses were corroborated by dispersion-corrected density functional calculations at the level of B97-D/def2-TZVPP. In CH2Cl2, 1-4 exhibit intramolecular charge-transfer (ICT) absorptions at 350-550 nm and green (lambda(em) similar to 540 nm) or orange (600 nm) fluorescence with high quantum yields (56-98%) and are more readily reduced than corannulene by up to 490 mV. The variation of optical gap and redox potentials of 1-4 does not correlate with the number of substituents. Cyanobutadienyl corannulenes 5-8 show red-shifted ICT absorptions with end-absorptions approaching 800 nm. Intersubstituent interactions lead to distortions of the corannulene core and lower the molecular symmetry. NMR, X-ray, and computational studies on 5 and 8 with one cyanobutadienyl substituent suggested the formation of intermolecular corannulene dimers. Bowl-inversion barriers around Delta G(double dagger) = 10-11 kcal/mol were determined for these two molecules.