5-(4-bromo-2,5-bis(dodecyloxy)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine | 264282-37-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-(4-bromo-2,5-bis(dodecyloxy)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine
• CAS: 264282-37-3
• 化学式: C₃₆H₅₇BrO₄S
• 分子量: 665.816
• InChiKey: ZLVXWIATRGMJKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.55
• 重原子数：
  42.0
• 可旋转键数：
  25.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  5-(4-bromo-2,5-bis(dodecyloxy)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine 在 正丁基锂 、 四甲基乙二胺 、 iron(III)-acetylacetonate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.0h， 以57%的产率得到7,7'-bis-(2,5-bis(dodecyloxy)phenyl)-2,2',3,3'-tetrahydro-5,5'-bithieno[3,4-b][1,4]dioxine
  参考文献：
  名称：

  Discrete Photopatternable π-Conjugated Oligomers for Electrochromic Devices

  摘要：

  Three discrete oligomeric systems including an all-thiophene (T6) system, a thiophene/phenylene (TPTTPT) system, and a thiophene/EDOT/phenylene (TPEEPT) system have been constructed and characterized with emphasis on structural, optical, electrochemical, and spectroelectrochemical properties. For all three chromophores, the radical cation, the dication, and the 7r-dimer have been identified and characterized. EPR spectroscopy reveals that the radical cations of TPTTPT and TPEEPT have g values of 2.008-2.012 and peak-to-peak widths in the range 4.2-5.3 G. Formation of the radical cation takes place at a lower potential for TPEEPT than for TPTTPT and T6, whereas subsequent oxidation to the dication occurs more easily for TPTTPT than for TPEEPT and T6. We ascribe this observation to more localized charges in the oxidized species of TPEEPT, which is supported by our finding that the radical cation of TPEEPT is less prone to undergo 7r-dimerization than the radical cations of TPTTPT and T6. All the oxidized species are sufficiently stable to allow for optical characterization, and the relative positions of all absorption bands are found to be in agreement with the electrochemical data. For further solid-state modifications of these materials, we have effectively modified the synthetic design and grafted terminal functionalities (e.s. acrylates) onto the discrete oligorners. Of these novel materials, TPEEPT proves to be the most promising anodically coloring material for electrochromics, and it undergoes reversible switching between two different colored states (bright yellow and clear blue) and one almost transparent and color neutral state. Contrast ratios, measured as 0%Tat Amax, are as high as 62.5%, and switching times are in the range 2-5 s for the coloration process, though significantly longer for the bleaching process. As a proof of concept, we have successfully constructed a simple photopatterned electrochromic device by exploiting the terminal acrylate functionalities of the oligomers in a UV-initiated cross-linking process. To the best of our knowledge, this is the first oligomer-based photopatterned electrochromic device reported in the literature.

  DOI：

  10.1021/ja7112273
• 作为产物：
  描述：

  1,4-二溴-2,5-二(十二烷氧基)苯 、 (2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)trimethylstannane 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以55%的产率得到5-(4-bromo-2,5-bis(dodecyloxy)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine
  参考文献：
  名称：

  Discrete Photopatternable π-Conjugated Oligomers for Electrochromic Devices

  摘要：

  Three discrete oligomeric systems including an all-thiophene (T6) system, a thiophene/phenylene (TPTTPT) system, and a thiophene/EDOT/phenylene (TPEEPT) system have been constructed and characterized with emphasis on structural, optical, electrochemical, and spectroelectrochemical properties. For all three chromophores, the radical cation, the dication, and the 7r-dimer have been identified and characterized. EPR spectroscopy reveals that the radical cations of TPTTPT and TPEEPT have g values of 2.008-2.012 and peak-to-peak widths in the range 4.2-5.3 G. Formation of the radical cation takes place at a lower potential for TPEEPT than for TPTTPT and T6, whereas subsequent oxidation to the dication occurs more easily for TPTTPT than for TPEEPT and T6. We ascribe this observation to more localized charges in the oxidized species of TPEEPT, which is supported by our finding that the radical cation of TPEEPT is less prone to undergo 7r-dimerization than the radical cations of TPTTPT and T6. All the oxidized species are sufficiently stable to allow for optical characterization, and the relative positions of all absorption bands are found to be in agreement with the electrochemical data. For further solid-state modifications of these materials, we have effectively modified the synthetic design and grafted terminal functionalities (e.s. acrylates) onto the discrete oligorners. Of these novel materials, TPEEPT proves to be the most promising anodically coloring material for electrochromics, and it undergoes reversible switching between two different colored states (bright yellow and clear blue) and one almost transparent and color neutral state. Contrast ratios, measured as 0%Tat Amax, are as high as 62.5%, and switching times are in the range 2-5 s for the coloration process, though significantly longer for the bleaching process. As a proof of concept, we have successfully constructed a simple photopatterned electrochromic device by exploiting the terminal acrylate functionalities of the oligomers in a UV-initiated cross-linking process. To the best of our knowledge, this is the first oligomer-based photopatterned electrochromic device reported in the literature.

  DOI：

  10.1021/ja7112273