2‐[2-(2‐{4‐[tris(4‐tert‐butylphenyl)methyl]phenoxy}ethoxy)ethoxy]ethanol | 351523-94-9

• 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: 2‐[2-(2‐{4‐[tris(4‐tert‐butylphenyl)methyl]phenoxy}ethoxy)ethoxy]ethanol
• 英文别名: 2-[2-[2-[4-[tris[4-(tert-butyl)phenyl]methyl]phenoxy]ethoxy]ethoxy]ethanol
• CAS: 351523-94-9
• 化学式: C₄₃H₅₆O₄
• 分子量: 636.915
• InChiKey: SCFNBOLGVWABOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.37
• 重原子数：
  47.0
• 可旋转键数：
  13.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2‐[2-(2‐{4‐[tris(4‐tert‐butylphenyl)methyl]phenoxy}ethoxy)ethoxy]ethanol 在 四溴化碳 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 49.0h， 以99%的产率得到2-[2-(2-{4-[tris(4-t-butylphenyl)methyl]phenoxy}ethoxy)ethoxy]ethyl bromide
  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：

  4-[tris-(4-tert-butylphenyl)methyl]phenol 、 三乙二醇 在 potassium hydroxide 作用下， 以 水 、 正丁醇 为溶剂， 反应 72.25h， 以75%的产率得到2‐[2-(2‐{4‐[tris(4‐tert‐butylphenyl)methyl]phenoxy}ethoxy)ethoxy]ethanol
  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

文献信息

• A copper-based shuttling [2]rotaxane with two bidentate chelates in the axis: steric control of the motion
  作者：Jean-Paul Collin、Fabien Durola、Jacques Lux、Jean-Pierre Sauvage

  DOI：10.1039/b9nj00296k

  日期：——

  most of the other molecular machines based on copper-complexed catenanes or rotaxanes made and investigated in Strasbourg, the present report is dealing with a molecular shuttle for which the copper centre is complexed to two bidentate chelates, regardless of the state of the shuttle. In other words, the axis contains a sterically hindering bidentate chelate, namely a 2,9-diphenyl-1,10-phenanthroline

  与大多数其他基于 铜-在斯特拉斯堡制造和研究的复杂的链烷或轮烷，本报告涉及一种分子穿梭，其铜中心与两个双齿螯合物络合，而与穿梭状态无关。换句话说，该轴包含位阻性双齿螯合物，即2,9-二苯基-1,10-菲咯啉 （dpp）衍生物，以及另一种但较少阻碍的双齿螯合物， 2,2'-联吡啶 （比比）。[2]轮烷的合成涉及15个单独的化学步骤，不包括[2]轮烷的大环组分的制备。带螺纹的大环是一个39元环，其中掺入了一个内环但非空间阻碍的螯合物。8,8'-联苯-3,3'-二异喹啉家庭（dpbiiq）。在循环伏安法时标（毫秒）上，铜络合物环从dpp“工位”到bipy“工位”的电化学诱导的滑动运动很快，反之亦然。这铜（I） 态最好位于dpp单元上，而通过氧化 铜（I） 中心移至其二价状态时，发生平移运动，以提供现在涉及双联螯合物的热力学上最稳定的状态。
• A Redox-Switchable Molecular Zipper
  作者：Melissa Dumartin、Mark C. Lipke、J. Fraser Stoddart

  DOI：10.1021/jacs.9b09756

  日期：2019.11.13

  each containing a 1,5-dioxynaphthalene ring. In its reduced state the ring-in-ring recognition motif, between the meta and para bisradical dicationic cyclophanes (rings) defines the [2]rotaxane, whereas in the oxidized state, the cyclobis(paraquat-4,4'-biphenylene) cyclophane encircles the two 1,5-dioxynaphthalene rings in the bifurcated 'tail'. The redox-controlled molecular shuttling, which can be likened

  显示复杂性增加的结构的人工分子开关 (AMS) 的设计和合成将在满足实现人工分子机器 (AMM) 的挑战性任务方面取得重大进展。在这里，我们报告了由环双（百草枯-4,4'-亚联苯基）环芳环和哑铃组成的分子穿梭的合成和表征，该哑铃包含环双（百草枯-间-亚苯基）环芳'头'和分叉的tawse - 像，“尾巴”由两个低聚醚链组成，每个链都包含一个 1,5-二氧萘环。在其还原状态下，在间位和对位双自由基双阳离子环芳烃（环）之间的环中识别基序定义了 [2] 轮烷，而在氧化状态下，环双（百草枯-4,4'-亚联苯）环芳烃包围两个1，分叉的“尾巴”中的 5-二氧萘环。氧化还原控制的分子穿梭，可以比作宏观世界中拉链的动作，表现出缓慢的动力学，受到分子穿梭分叉“尾巴”的打开和关闭的抑制。循环伏安法表明这种缓慢穿梭与电化学滞后有关。
• A Fast-Moving Copper-Based Molecular Shuttle: Synthesis and Dynamic Properties
  作者：Fabien Durola、Jacques Lux、Jean-Pierre Sauvage

  DOI：10.1002/chem.200802510

  日期：2009.4.14

  Fast‐track changes: The synthesis of a new copper‐based molecular shuttle is described, with a coordinating macrocycle based on a nonhindering but endocyclic ligand (see scheme), which makes the ligand exchange easier, and thus the motions of the ring along the thread faster.

  快速变化：描述了一种新的基于铜的分子穿梭的合成，并基于一个无阻碍但有环内配体的配位大环（参见方案），这使配体的交换变得更加容易，从而使环沿环的运动更加容易。线程速度更快。
• A Rapidly Shuttling Copper-Complexed [2]Rotaxane with Three Different Chelating Groups in Its Axis
  作者：Jean-Paul Collin、Fabien Durola、Jacques Lux、Jean-Pierre Sauvage

  DOI：10.1002/anie.200903311

  日期：2009.10.26

  of a copper‐complexed [2]rotaxane incorporates an endocyclic but nonsterically hindering bidentate chelate. The rotaxane axis contains three different chelates (see picture), and both terminal coordination sites are separated by about 23 Å. The shuttling motion is triggered by oxidation or reduction of the copper center and is as fast as that in a related two‐station rotaxane whose terminal stations

  速度与激情：铜络合物[2]轮烷的移动环结合了一个内环但非空间阻碍双齿螯合物的环。轮烷的轴包含三种不同的螯合物（见图），并且两个末端配位点之间的间隔约为23Å。穿梭运动是由铜中心的氧化或还原触发的，其速度与相关的两站式轮烷的速度一样，后者的末端站相距10Å。