3,3'''-(1,13-dithia-4,7,10-trioxa-1,13-tridecanediyl)-2,2':5',2'':5'':2'''-quaterthiophene

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,3'''-(1,13-dithia-4,7,10-trioxa-1,13-tridecanediyl)-2,2':5',2'':5'':2'''-quaterthiophene
• 英文别名: 14,17,20-Trioxa-7,11,23,27,32,33-hexathiapentacyclo[27.2.1.12,5.06,10.024,28]tritriaconta-1(31),2,4,6(10),8,24(28),25,29-octaene；14,17,20-trioxa-7,11,23,27,32,33-hexathiapentacyclo[27.2.1.12,5.06,10.024,28]tritriaconta-1(31),2,4,6(10),8,24(28),25,29-octaene
• 化学式: C₂₄H₂₄O₃S₆
• 分子量: 552.849
• InChiKey: BCDOYDVOLCOJSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  33
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  191
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  双[2-(2-氯化乙氧基)乙基]醚 在 sodium iodide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 112.5h， 生成 3,3'''-(1,13-dithia-4,7,10-trioxa-1,13-tridecanediyl)-2,2':5',2'':5'':2'''-quaterthiophene
  参考文献：
  名称：

  Crown-Annelated Oligothiophenes as Model Compounds for Molecular Actuation

  摘要：

  Crown-annelated quater- (4T) and sexithiophenes (6T) with oligooxyethylene chains of various lengths attached at the 3-positions of the terminal thiophene rings have been synthesized. Analysis of the cation-binding properties of the macrocycles by H-1 NMR and UV-vis spectroscopy reveals the formation of a 1:1 complex with Ba2+, Sr2+, or Pb2+ and shows that cation complexation results in a conformational transition in the pi-conjugated system. Theoretical analysis of this process by density functional methods predicts that this conformational transition results in a narrowing of the highest occupied-lowest unoccupied molecular orbital gap of the conjugated system with a decrease of the redox potentials (E-1(0) and E-2(0)) associated with the formation of the 4T cation radical and dication. Cyclic voltarmmetry shows that, depending on the binding constant, the presence of metal cation produces a negative or a positive shift of E-1(0) while E-2(0) always shifts negatively. This unusual behavior is discussed in terms of interplay between electrostatic interactions and conformational changes associated with cation binding.

  DOI：

  10.1021/ja026819p

文献信息

• Crown-Annelated Oligothiophenes as Model Compounds for Molecular Actuation
  作者：Bruno Jousselme、Philippe Blanchard、Eric Levillain、Jacques Delaunay、Magali Allain、Pascal Richomme、David Rondeau、Nuria Gallego-Planas、Jean Roncali

  DOI：10.1021/ja026819p

  日期：2003.2.1

  Crown-annelated quater- (4T) and sexithiophenes (6T) with oligooxyethylene chains of various lengths attached at the 3-positions of the terminal thiophene rings have been synthesized. Analysis of the cation-binding properties of the macrocycles by H-1 NMR and UV-vis spectroscopy reveals the formation of a 1:1 complex with Ba2+, Sr2+, or Pb2+ and shows that cation complexation results in a conformational transition in the pi-conjugated system. Theoretical analysis of this process by density functional methods predicts that this conformational transition results in a narrowing of the highest occupied-lowest unoccupied molecular orbital gap of the conjugated system with a decrease of the redox potentials (E-1(0) and E-2(0)) associated with the formation of the 4T cation radical and dication. Cyclic voltarmmetry shows that, depending on the binding constant, the presence of metal cation produces a negative or a positive shift of E-1(0) while E-2(0) always shifts negatively. This unusual behavior is discussed in terms of interplay between electrostatic interactions and conformational changes associated with cation binding.