trans-4,4'-azophenyl-p-phenylene-p-phenylene-57-crown-15 | 224298-59-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-4,4'-azophenyl-p-phenylene-p-phenylene-57-crown-15
• CAS: 224298-59-3
• 化学式: C₄₈H₆₄N₂O₁₅
• 分子量: 909.041
• InChiKey: RLOSHSAQCKCZRR-BNEIJSFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.94
• 重原子数：
  65.0
• 可旋转键数：
  0.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  163.17
• 氢给体数：
  0.0
• 氢受体数：
  17.0

反应信息

• 作为反应物：
  描述：

  1,4-二(溴甲基)苯 、 1,1-[1,4-phenylenebis(methylene)]bis-4,4'-pyridylpiridinium bis(hexafluorophosphate) 、 trans-4,4'-azophenyl-p-phenylene-p-phenylene-57-crown-15 以 N,N-二甲基甲酰胺 为溶剂， 反应 336.0h， 以30%的产率得到
  参考文献：
  名称：

  Photoactive Azobenzene-Containing Supramolecular Complexes and Related Interlocked Molecular Compounds

  摘要：

  Two acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4'-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene)-a tetracationic cyclophane-in their trans forms only. On irradiation (lambda = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4'-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (lambda = 440 nm) or by warming the solution in the dark. Variable temperature H-1 NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4'-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4'-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (lambda=360 nm) from the trans to the cis isomer of the 4,4'-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4'-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<860::aid-chem860>3.0.co;2-k
• 作为产物：
  描述：

  4,4'-bis<2-<2-<2-(2-hydroxyethoxy)ethoxy>ethoxy>ethoxy>azobenzene 在 sodium hydroxide 、 caesium carbonate 、 cesium 4-methylbenzenesulfonate 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 192.0h， 生成 trans-4,4'-azophenyl-p-phenylene-p-phenylene-57-crown-15
  参考文献：
  名称：

  Photoactive Azobenzene-Containing Supramolecular Complexes and Related Interlocked Molecular Compounds

  摘要：

  Two acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4'-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene)-a tetracationic cyclophane-in their trans forms only. On irradiation (lambda = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4'-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (lambda = 440 nm) or by warming the solution in the dark. Variable temperature H-1 NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4'-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4'-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (lambda=360 nm) from the trans to the cis isomer of the 4,4'-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4'-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<860::aid-chem860>3.0.co;2-k