2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methylenoxymethylenyl]-1,10-phenanthroline | 223244-38-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methylenoxymethylenyl]-1,10-phenanthroline
• 英文别名: 2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methoxymethyl]-1,10-phenanthroline；2,9-Bis[[6-(6-methylpyridin-2-yl)pyridin-2-yl]methoxymethyl]-1,10-phenanthroline
• CAS: 223244-38-0
• 化学式: C₃₈H₃₂N₆O₂
• 分子量: 604.711
• InChiKey: ZOLXFPNVKOZGQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  46
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  95.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  tetrakis(actonitrile)copper(I) hexafluorophosphate 、 2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methylenoxymethylenyl]-1,10-phenanthroline 以 乙腈 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  金属的双（联吡啶）-菲咯啉双链螺旋产物：锌（II），银（I）和铜（I）螺旋

  摘要：

  制备了新的配体2,9-双[（6-甲基-2,2'-联吡啶-6'-基）亚甲氧基亚甲基-基] -1,10-菲咯啉（1）并显示其自组装成双与Cu +，Ag +和Zn 2+反应生成双链螺旋盐，从而得到第一个三核双链螺旋锌盐。[（1）2 M 3 ] 3 n + [M = Cu +（n = 1），Ag +（n = 1）或Zn 2+（n= 2）]螺旋产物通过1D，2D和扩散NMR进行表征。FAB质谱证实了银和螺旋铜的结构，并通过X射线晶体学表征了[（1）2 Cu 3 ] 3+。这些螺旋体的1 H NMR光谱的详细分配显示，与这些配合物的其他质子相比，H-10的吸收场高得多。这种高场偏移是1的螺旋结构的独特特征，在结构相关的螺旋结构中未发现。这些螺旋体的NMR光谱在室温下与具有D 2的平均溶液结构一致对称。可变温度1 H NMR（VT-NMR）揭示1的螺旋状银比其螺旋状的铜更不稳定。从VT-NMR光谱看来，在[（1）2

  DOI：

  10.1039/a808673g
• 作为产物：
  描述：

  6-(bromomethyl)-6'-methyl-2,2'-bipyridine 、 2,9-二羟甲基-1,10-菲啰啉 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 120.0h， 以34%的产率得到2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methylenoxymethylenyl]-1,10-phenanthroline
  参考文献：
  名称：

  From Homoleptic to Heteroleptic Double Stranded Copper(I) Helicates:  The Role of Self-Recognition in Self-Assembly Processes

  摘要：

  The Ligands 2,9-bis[(6-methyl-2,2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6 ",6'''-bis[(6-methyl-2,2'-bipyridin-6'-yl)methleneoxymethylenyl)]-2 ",2'''-bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl -2,2'-bithiophene (7), and 6,6'-bisT(6-methyl-2,2'-bipyridin-6'-yl)methyleneoxymethylenyl] -2,2'-biphenyl (8) and their respective homo - and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu-3](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu-3](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu-2](2+) complexes. The potential shift, Delta E degrees of the Cu+/Cu2+ redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu+ as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cut. Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.

  DOI：

  10.1021/jo991469j