14,14,23,23-Tetraphenyl-8,29-dioxahexacyclo[29.2.2.23,6.217,20.19,13.124,28]hentetraconta-1(33),3(41),4,6(40),9,11,13(39),17(38),18,20(37),24(36),25,27,31,34-pentadecaen-15,21-diyn-2-one | 1338248-43-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 14,14,23,23-Tetraphenyl-8,29-dioxahexacyclo[29.2.2.23,6.217,20.19,13.124,28]hentetraconta-1(33),3(41),4,6(40),9,11,13(39),17(38),18,20(37),24(36),25,27,31,34-pentadecaen-15,21-diyn-2-one
• CAS: 1338248-43-3
• 化学式: C₆₃H₄₄O₃
• 分子量: 849.041
• InChiKey: AYBTYVRENBCBQB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.2
• 重原子数：
  66
• 可旋转键数：
  4
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  14,14,23,23-Tetraphenyl-8,29-dioxahexacyclo[29.2.2.23,6.217,20.19,13.124,28]hentetraconta-1(33),3(41),4,6(40),9,11,13(39),17(38),18,20(37),24(36),25,27,31,34-pentadecaen-15,21-diyn-2-one 以 异丙醇 、 苯 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  具有聚集诱导发射荧光团的结晶分子转子的荧光和旋转动力学

  摘要：

  最近的研究表明，快速构象运动形式的“晶体流动性”对于晶体中的大振幅旋转运动至关重要。为了探索这一概念，我们设计了一个晶体组件，该组件具有两个与四苯基乙烯（TPE）连接的二乙炔基苯（DEB）分子旋转器，四苯基乙烯（TPE）是一种荧光团，其发射强度取决于介质的刚度。我们预想，随着温度的升高，晶体流动性的增加将有利于DEB的旋转运动，同时减小TPE的荧光强度。当通过向THF溶液中添加水而增加其荧光强度时，证实了TPE部分的聚集诱导的发射。虽然散装固体显示出相对较强的TPE发射，寿命为4±1 ns，在从77 K到298 K的测量之间没有观察到显着变化，表明晶体环境在激发态寿命内的运动受到限制。四极回波证实了这一结论氘标记的样品在198和298 K之间的2 H NMR线形分析显示了微秒状态下的旋转相关时间，表明旋转流动性太慢3个数量级，以至于无法影响荧光发射。

  DOI：

  10.1021/acs.joc.9b01201
• 作为产物：
  描述：

  间溴苯甲醚 在 copper(l) iodide 、 正丁基锂 、 trans-bis(triphenylphosphine)palladium dichloride 、 三溴化硼 、 potassium carbonate 、 二异丙胺 、 乙酰氯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 28.5h， 生成 14,14,23,23-Tetraphenyl-8,29-dioxahexacyclo[29.2.2.23,6.217,20.19,13.124,28]hentetraconta-1(33),3(41),4,6(40),9,11,13(39),17(38),18,20(37),24(36),25,27,31,34-pentadecaen-15,21-diyn-2-one
  参考文献：
  名称：

  Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization

  摘要：

  We describe the synthesis and characterization of six bridged molecular gyroscopes with m-alkoxy-substituted trityl stators and dialkynylphenylene rotators. All of the bridged molecular gyroscopes were synthesized convergently to form the phenolic stator-rotator framework, while the alkyl and benzophenone bridges were installed in one step by relatively efficient one-pot reactions to form macrocyclic diether or diester linkages. The isolated yield per bond-forming reaction varied from ca. 42% to 80%, with one exception where macrocyclization failed to produce the desired product. The molecular structure and crystal packing of each of the bridged molecular gyroscopes were determined via single crystal X-ray diffraction. Like most molecular gyroscopes with open topologies previously studied, the singly bridged structures pack by interdigitating one trityl stator in one molecule next to the rotator of an adjacent molecule in the lattice. In contrast, the triply bridged molecular gyroscopes were found to pack in lamellar sheets that prevent the rotator-stator interdigitation of adjacent molecules. However, solvent molecules and conformationally flexible bridges tend to fill in the packing volume by collapsing next to the rotator or by extending one of their bridges into the cavity of a neighboring molecule.

  DOI：

  10.1021/jo201513y

文献信息

• Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization
  作者：Patrick Commins、Jose E. Nuñez、Miguel A. Garcia-Garibay

  DOI：10.1021/jo201513y

  日期：2011.10.21

  We describe the synthesis and characterization of six bridged molecular gyroscopes with m-alkoxy-substituted trityl stators and dialkynylphenylene rotators. All of the bridged molecular gyroscopes were synthesized convergently to form the phenolic stator-rotator framework, while the alkyl and benzophenone bridges were installed in one step by relatively efficient one-pot reactions to form macrocyclic diether or diester linkages. The isolated yield per bond-forming reaction varied from ca. 42% to 80%, with one exception where macrocyclization failed to produce the desired product. The molecular structure and crystal packing of each of the bridged molecular gyroscopes were determined via single crystal X-ray diffraction. Like most molecular gyroscopes with open topologies previously studied, the singly bridged structures pack by interdigitating one trityl stator in one molecule next to the rotator of an adjacent molecule in the lattice. In contrast, the triply bridged molecular gyroscopes were found to pack in lamellar sheets that prevent the rotator-stator interdigitation of adjacent molecules. However, solvent molecules and conformationally flexible bridges tend to fill in the packing volume by collapsing next to the rotator or by extending one of their bridges into the cavity of a neighboring molecule.
• Fluorescence and Rotational Dynamics of a Crystalline Molecular Rotor Featuring an Aggregation-Induced Emission Fluorophore
  作者：Morgan E. Howe、Miguel A. Garcia-Garibay

  DOI：10.1021/acs.joc.9b01201

  日期：2019.8.2

  tetraphenylethylene (TPE), a fluorophore known to emit with intensities that depend on the rigidity of the medium. We envisioned that an increase in crystal fluidity as a function of increasing temperature would facilitate rotational motion of the DEB while diminishing the fluorescence intensity of the TPE. The aggregation-induced emission of the TPE moiety was confirmed when its fluorescence intensity increased

  最近的研究表明，快速构象运动形式的“晶体流动性”对于晶体中的大振幅旋转运动至关重要。为了探索这一概念，我们设计了一个晶体组件，该组件具有两个与四苯基乙烯（TPE）连接的二乙炔基苯（DEB）分子旋转器，四苯基乙烯（TPE）是一种荧光团，其发射强度取决于介质的刚度。我们预想，随着温度的升高，晶体流动性的增加将有利于DEB的旋转运动，同时减小TPE的荧光强度。当通过向THF溶液中添加水而增加其荧光强度时，证实了TPE部分的聚集诱导的发射。虽然散装固体显示出相对较强的TPE发射，寿命为4±1 ns，在从77 K到298 K的测量之间没有观察到显着变化，表明晶体环境在激发态寿命内的运动受到限制。四极回波证实了这一结论氘标记的样品在198和298 K之间的2 H NMR线形分析显示了微秒状态下的旋转相关时间，表明旋转流动性太慢3个数量级，以至于无法影响荧光发射。