hexakis(3,4-dicyanophenyl)[3]radialene | 1372196-16-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: hexakis(3,4-dicyanophenyl)[3]radialene
• 英文别名: 4-[[2,3-Bis[bis(3,4-dicyanophenyl)methylidene]cyclopropylidene]-(3,4-dicyanophenyl)methyl]benzene-1,2-dicarbonitrile；4-[[2,3-bis[bis(3,4-dicyanophenyl)methylidene]cyclopropylidene]-(3,4-dicyanophenyl)methyl]benzene-1,2-dicarbonitrile
• CAS: 1372196-16-1
• 化学式: C₅₄H₁₈N₁₂
• 分子量: 834.817
• InChiKey: KRKBKSFTJJUIPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  66
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  286
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  hexakis(3,4-dicyanophenyl)[3]radialene 在 四丁基溴化铵 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Anion−π Interactions of Hexaaryl[3]radialenes

  摘要：

  Coordination polymers and discrete metallo-supramolecular assemblies of hexaaryl[3]radialene compounds exhibit intriguing structures with short anion to pi-centroid distances in the solid-state. Furthermore, these [3]radialene compounds display useful photophysical and electrochemical properties that make them ideal as potential platforms for anion receptors. In this study, hexafluoro[3]radialene was optimized to the MP2/aug-cc-pVTZ level of theory, and its complexes with halide anions were optimized to HF/6-31G+ +(d,p), MP2/6-31G++(d,p), M06-2X/6-31G++(d,p), and M06-2X/6-311G++(d,p) levels of theory. Hexafluoro[3]radialene was shown to have properties (large positive Q(zz) and areas of positive electrostatic surface potential) comparable to other compounds that show anion-pi interactions. The interaction energies of complexes of hexafluoro[3]radialene with halide anions were calculated and found to be favorable and equivalent to those of fluorinated aromatic compounds. A series of synthetically accessible hexaaryl[3]radialenes were optimized to HF/6-31G++(d,p) theory and their complexes with halides optimized to the M06-2X/6-31G++(d,p) level of theory. The calculated properties of the electron-deficient hexaaryl[3]radialenes also show large positive Q(zz) quadrupole moments and two areas of positive potential; at the [3]radialene core and the acidic aryl hydrogen atoms. The interaction energies of the complexes of hexaaryl[3]radialenes and halide anions were found to follow the trend F- > Cl- approximate to Br- and correlate with the electron-deficient nature of the [3]radialene. Close contacts were observed between the anion and the radialene core and the aryl hydrogen atoms, suggesting a combination of anion-pi and hydrogen bonding is important. Mass spectrometry was used to experimentally observe the complexes of a number of hexaaryl[3]radialenes with F-, Cl-, and Br- predicted computationally. Anion-[3]radialene complexes were successfully detected, and the stability of the complexes in tandem MS/MS experiments was found to support the computational results.

  DOI：

  10.1021/jp301464s
• 作为产物：
  描述：

  二苯基甲烷-3,3',4,4'-四羧酸 在 ammonium hydroxide 、 氯化亚砜 、 sodium hydride 、 formamide 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 100.5h， 生成 hexakis(3,4-dicyanophenyl)[3]radialene
  参考文献：
  名称：

  荧光六芳基和六杂芳基 [3] radialenes：合成、结构和性质。

  摘要：

  报道了三种新的 [3] radialene - hexakis(3,5-二甲基吡唑基)-、hexakis(3-cyanophenyl)-和 hexakis(3,4-dicyanophenyl)[3]radialene (1-3)-的合成。化合物3分五步得到，关键步骤收率为76%。与此相比，合成1和2的各个步骤导致较低的产率。所有化合物在溶液中均采用双叶螺旋桨构象。化合物 3 比先前报道的六芳基 [3] radialenes 缺电子得多，在 CH(2)Cl(2) 中的还原电位为 -0.06 和 -0.45 V。这些化合物大多显示具有大斯托克斯位移的红色荧光。

  DOI：

  10.3762/bjoc.8.7

文献信息

• Fluorescent hexaaryl- and hexa-heteroaryl[3]radialenes: Synthesis, structures, and properties
  作者：Antonio Avellaneda、Courtney A Hollis、Xin He、Christopher J Sumby

  DOI：10.3762/bjoc.8.7

  日期：——

  The syntheses of three new [3]radialenes - hexakis(3,5-dimethylpyrazolyl)-, hexakis(3-cyanophenyl)-, and hexakis(3,4-dicyanophenyl)[3]radialene (1-3) - are reported. Compound 3 is obtained in five steps with an excellent yield of 76% in the key step. Compared to that, the respective steps of the syntheses of 1 and 2 result in lower yields. All compounds adopt a double bladed propeller conformation

  报道了三种新的 [3] radialene - hexakis(3,5-二甲基吡唑基)-、hexakis(3-cyanophenyl)-和 hexakis(3,4-dicyanophenyl)[3]radialene (1-3)-的合成。化合物3分五步得到，关键步骤收率为76%。与此相比，合成1和2的各个步骤导致较低的产率。所有化合物在溶液中均采用双叶螺旋桨构象。化合物 3 比先前报道的六芳基 [3] radialenes 缺电子得多，在 CH(2)Cl(2) 中的还原电位为 -0.06 和 -0.45 V。这些化合物大多显示具有大斯托克斯位移的红色荧光。
• Anion−π Interactions of Hexaaryl[3]radialenes
  作者：Jack D. Evans、Courtney A. Hollis、Sandra Hack、Alexander S. Gentleman、Peter Hoffmann、Mark A. Buntine、Christopher J. Sumby

  DOI：10.1021/jp301464s

  日期：2012.8.2

  Coordination polymers and discrete metallo-supramolecular assemblies of hexaaryl[3]radialene compounds exhibit intriguing structures with short anion to pi-centroid distances in the solid-state. Furthermore, these [3]radialene compounds display useful photophysical and electrochemical properties that make them ideal as potential platforms for anion receptors. In this study, hexafluoro[3]radialene was optimized to the MP2/aug-cc-pVTZ level of theory, and its complexes with halide anions were optimized to HF/6-31G+ +(d,p), MP2/6-31G++(d,p), M06-2X/6-31G++(d,p), and M06-2X/6-311G++(d,p) levels of theory. Hexafluoro[3]radialene was shown to have properties (large positive Q(zz) and areas of positive electrostatic surface potential) comparable to other compounds that show anion-pi interactions. The interaction energies of complexes of hexafluoro[3]radialene with halide anions were calculated and found to be favorable and equivalent to those of fluorinated aromatic compounds. A series of synthetically accessible hexaaryl[3]radialenes were optimized to HF/6-31G++(d,p) theory and their complexes with halides optimized to the M06-2X/6-31G++(d,p) level of theory. The calculated properties of the electron-deficient hexaaryl[3]radialenes also show large positive Q(zz) quadrupole moments and two areas of positive potential; at the [3]radialene core and the acidic aryl hydrogen atoms. The interaction energies of the complexes of hexaaryl[3]radialenes and halide anions were found to follow the trend F- > Cl- approximate to Br- and correlate with the electron-deficient nature of the [3]radialene. Close contacts were observed between the anion and the radialene core and the aryl hydrogen atoms, suggesting a combination of anion-pi and hydrogen bonding is important. Mass spectrometry was used to experimentally observe the complexes of a number of hexaaryl[3]radialenes with F-, Cl-, and Br- predicted computationally. Anion-[3]radialene complexes were successfully detected, and the stability of the complexes in tandem MS/MS experiments was found to support the computational results.