1'1'''-dibenzyl-1,1''-1,4-phenylene-bis(methylene)bis-4,4'-bipyridinetetraium-tetrakis(hexafluorophosphate) | 108861-27-4

• 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: 1'1'''-dibenzyl-1,1''-1,4-phenylene-bis(methylene)bis-4,4'-bipyridinetetraium-tetrakis(hexafluorophosphate)
• CAS: 108861-27-4
• 化学式: C₄₂H₃₈N₄*4F₆P
• 分子量: 1178.65
• InChiKey: FKUWXDQKXBDACG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.75
• 重原子数：
  53.0
• 可旋转键数：
  10.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  15.52
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,1''-[1,4-phenylenebis(methylene)]bis[1'-(phenylmethyl)-4,4'-bipyridinium] tetrabromide 在 ammonium hexafluorophosphate 作用下， 以 水 为溶剂， 生成 1'1'''-dibenzyl-1,1''-1,4-phenylene-bis(methylene)bis-4,4'-bipyridinetetraium-tetrakis(hexafluorophosphate)
  参考文献：
  名称：

  单桥和双桥成色剂及其阳离子自由基的分子内二聚化

  摘要：

  作为我们对可逆氧化还原系统研究的扩展，已合成了六种四季盐。这些化合物包含两个4,4'-联吡啶鎓单元，它们通过一个或两个刚性桥连接。单桥系统（o-，m -3，p -3）包含一个o-，m-或对亚二甲苯基桥。双桥系统（o，o -4，o，m -4和m，m-4）包含两个亚二甲苯基桥，代表一类新的环烷。描述了用于合成这些化合物的新的且非常简单的高稀释技术。根据环的大小，某些系统在桥的翻转和吡啶环的旋转方面显示出不同的内部迁移率。通过化合物3和4的伏安法，仅观察到预期的四个电位中的两个或三个。这可能是由于高度稳定的双基指示3 SEM / SEM和4 SEM / SEM所致。通过对阳离子自由基的浓度和温度相关的UV / VIS光谱进行研究，得出平衡常数K 1和K 2。评估了分子内和分子间二聚化（CT络合）的热力学数据。用o -3 SEM / SEM和o，o -4 SEM / SEM观察到最强的分子内二聚体作用，它们仅以嵌体形式存在。

  DOI：

  10.1016/s0040-4020(01)87583-9

文献信息

• Catenane and inclusion complex as photochromic compounds involving viologen units
  作者：Tetsuo Kuwabara、Maki Sugiyama、Kazutoshi Takeuchi、Hideto Sakane

  DOI：10.1016/j.jphotochem.2013.07.002

  日期：2013.10

  Catenane (1) consisting of a tetracationic cyclophane (2) and p-benzocrown ether (5) has been prepared to investigate its photochromic behavior in a poly(N-vinyl-2-pyrroridone) (PVP) film by comparing with that of 2 in the absence and the presence of pi-electron donating guests such as indole (6) and p-dimethoxybenzene (7). The PVP film containing I showed a red color due to the pi-donor/pi-acceptor charge transfer interaction between the viologen and the dialkoxybenezene units in 1. Upon photoirradiation the film changed the color to blue with the absorption maximum (lambda(max)) at 620 nm, associated with the photoreduction of the viologen unit from the dication to the radical cation, and reverted to the original dication with the half-life (tau(1/2)) of 15 min. The pale yellow film containing 2 showed the similar photochromic behavior to that of 1 with lambda(max) at 610 nm and tip at tau(1/2) min, which are shifted to blue side by 10 nm and to longer time by 9 min as compared with those of 1. The difference in the photochromic behavior between 1 and 2 is resulted from the existence of the pi-electron donating unit, 5, which is interlocked with the ring of 2 in the compound 1. The effect of the pi-electron donating unit on the photochromic behavior of viologen was confirmed by the addition of 6 and 7 to the film containing 2 or its acyclic analog, 3. The lambda(max) and tau(1/2) for the photoreduced 2 were observed at 620 nm and 14 min, and at 615 nm and 20 min in the presence of 6 and 7, respectively. The larger effect of 6 rather than 7 on the photochromic properties of 2 was interpreted in terms of the larger binding constant of 6 with 2 than that of 7 in dimethylacetamide (DMAc) (3.0 and 2.3 M-1 for 6 and 7, respectively). The addition of 6 and 7 to the film containing 3 caused no change in the photochromic properties of 3 (lambda(max)=611 nm and tau(1/2)=22 min). When the simple benzylviologen (4) was used as the photochromic compound, the reversion rate of the photoreduced 4 was accelerated by the addition of 5 but it was not accelerated by 7. All these results demonstrate that the cyclic structure as well as the catenane promote the strong interaction between viologen and pi-electron donating units. The interaction leads the change not only in color of the film before photoirradiation but also in the photochromic behaviors of viologen derivatives. (C) 2013 Elsevier B.V. All rights reserved.