| 1596368-59-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 1596368-59-0
• 化学式: C₃₆H₃₂N₄*C₉₂H₁₁₂O₄S₈
• 分子量: 2059.1
• InChiKey: BGLLHKRFTMVQNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  31.99
• 重原子数：
  144.0
• 可旋转键数：
  29.0
• 环数：
  32.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.44
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  在 锌 作用下， 以 氘代乙腈 为溶剂， 生成
  参考文献：
  名称：

  Mechanistic Evaluation of Motion in Redox-Driven Rotaxanes Reveals Longer Linkers Hasten Forward Escapes and Hinder Backward Translations

  摘要：

  Mechanistic understanding of the translational movements in molecular switches is essential for designing machine-like prototypes capable of following set pathways of motion. To this end, we demonstrated that increasing the station-to-station distance will speed up the linear movements forward and slow down the movements backward in a homologous series of bistable rotaxanes. Four redox-active rotaxanes, which drove a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) mobile ring between a tetrathiafulvalene (TTF) station and an oxyphenylene station, were synthesized with only variations to the lengths of the glycol linker connecting the two stations (n = 5, 8, 11, and 23 atoms). We undertook the first mechanistic study of the full cycle of motion in this class of molecular switch using cyclic voltammetry. The kinetics parameters (k, Delta G(double dagger) of switching were determined at different temperatures to provide activation enthalpies (Delta H-double dagger) and entropies (Delta S-double dagger). Longer glycol linkers led to modest increases in the forward escape (t(1/2) = 60 to <7 ms). The rate-limiting step involves movement of the tetracationic CBPQT(4+) ring away from the singly oxidized TTF+ unit by overcoming one of the thiomethyl (SMe) speed bumps before proceeding on to the secondary oxyphenylene station. Upon reduction, however, the return translational movement of the CBPQT(4+) ring from the oxyphenylene station back to the neutral TTF station was slowed considerably by the longer linkers (t(1/2) = 1.4 to >69 s); though not because of a diffusive walk. The reduced rate of motion backward depended on folded structures that were only present with longer linkers.

  DOI：

  10.1021/ja5013596
• 作为产物：
  描述：

  在 iron(III) perchlorate 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  盐加速环双（百草枯-对苯撑）[2]轮烷的转换动力学

  摘要：

  发现在添加盐的存在下，双稳态[2]轮烷的大环环双（百草枯对苯撑）环在四硫富瓦烯键氧化时从四硫富瓦烯键移至氧亚苯基键的速率增加了。与无盐情况相比，一系列六氟磷酸四烷基铵盐（R 4 N·PF 6，R = H，Me，Et或n -Bu）和高氯酸四丁铵（n -Bu 4 N·ClO ）的溶液为0.1 M 4）都提高了开关速度，这在n -Bu 4 N·ClO 4情况下最大与较小的阴离子。铵阳离子大小的变化没有明显影响。这些结果表明，过量的离子的添加​​可以用作促进剂，以基于可移动的环双（百草枯-对苯撑）环加快轮烷和链烷中的穿梭过程，并且阴离子的选择提供了一种方便的控制方法这种影响的程度。

  DOI：

  10.1039/c9ob00085b