4-formyl-1-trimethylethynyl-2,5-dioctyloxybenzene | 585567-29-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-formyl-1-trimethylethynyl-2,5-dioctyloxybenzene
• 英文别名: 2,5-dioctyloxy-4-trimethylsilylethynylbenzaldehyde；2,5-Bis(octyloxy)-4-[(trimethylsilyl)ethynyl]benzaldehyde；2,5-dioctoxy-4-(2-trimethylsilylethynyl)benzaldehyde
• CAS: 585567-29-9
• 化学式: C₂₈H₄₆O₃Si
• 分子量: 458.757
• InChiKey: APYVQVXHNXOZHL-UHFFFAOYSA-N

物化性质

• 沸点：
  543.4±50.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.21
• 重原子数：
  32
• 可旋转键数：
  19
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  4-formyl-1-trimethylethynyl-2,5-dioctyloxybenzene 在 四(三苯基膦)钯 potassium fluoride 、 copper(l) iodide 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 30.0h， 生成 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)butadiyne-1,3
  参考文献：
  名称：

  Supramolecular Ordering, Thermal Behavior, and Photophysical, Electrochemical, and Electroluminescent Properties of Alkoxy-Substituted Yne-Containing Poly(phenylene−vinylene)s

  摘要：

  Alkoxy-substituted and defect-free yne-containing poly(phenylene-vinylene)s, 15a-d, having the general constitutional unit (-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-) synthesized through the olefination reactions of the fluorophoric dialdehyde 7 [1,2-bis(4-formyl-2,5-dialkoxyphenyl)acetylene] with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 14a-d, are reported. A new synthetic route to 1-bromo-2,5-dialkoxybenzaldehyde (starting material for the synthesis of 7) allowing the grafting of all types of alkoxy side chains is also reported. Bulk state properties of the four polymeric materials have been analyzed using various experimental methods giving information on the thermal behavior as well as self-assembling morphologies at different size scales. Crystalline superstructures of either spherulitic or rodlike morphology, comprised of polymeric backbone layers separated by the side chains are identified to develop by nucleation and growth process for symmetrically alkoxy substituted 15a-c. Discrepancy between optical (E-g(opt)) and electrochemical (E-g(ee)) band gaps was observed to be dependent on the bulkiness (15c) and length (15b) of the grafted side chains. Octadecyloxy side chains in 15b not only lead to well structured photoluminescence and electroluminescence spectra and higher fluorescence quantum yields but also allow the design of LED-devices of the configuration ITO/PEDOT/polymer/Ca with improved parameters (eta(ext) = 2.15%, luminance = 5760 cd/m(2)) relative to the octyloxy-substituted polymer 15a (eta(ext) = 0.79%, luminance = 1406 cd/m(2)). Despite the differences in the conjugation pattern between polymers 15 and polymers 17 [(-Ph-CdropC-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-)], an identical chromophore system of structure Ph-CdropC-Ph-CH=CH-Ph-CH=CH-Ph-CdropC-Ph was found to be responsible for their emissive behavior as confirmed by fluorescence kinetics measurements (tau, k(f), k(nr)) and quantum chemical calculations. The differences observed in their solid-state photophysical properties are ascribed to the combined effects of the backbone rigidity (as a function of the number of -CdropC- moieties in the repeating unit) and the nature of the side chains. Moreover less -CdropC- units within polymers 15 lead to the more than 100-fold improvement of their electroluminescent parameters compared to polymers 17.

  DOI：

  10.1021/ma0488111
• 作为产物：
  描述：

  溴羟基喹啉 在 四(三苯基膦)钯 氢氧化钾 、 copper(l) iodide 、 硫酸 、 溶剂黄146 、 二异丙胺 、 pyridinium chlorochromate 、 sodium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 44.5h， 生成 4-formyl-1-trimethylethynyl-2,5-dioctyloxybenzene
  参考文献：
  名称：

  Supramolecular Ordering, Thermal Behavior, and Photophysical, Electrochemical, and Electroluminescent Properties of Alkoxy-Substituted Yne-Containing Poly(phenylene−vinylene)s

  摘要：

  Alkoxy-substituted and defect-free yne-containing poly(phenylene-vinylene)s, 15a-d, having the general constitutional unit (-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-) synthesized through the olefination reactions of the fluorophoric dialdehyde 7 [1,2-bis(4-formyl-2,5-dialkoxyphenyl)acetylene] with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 14a-d, are reported. A new synthetic route to 1-bromo-2,5-dialkoxybenzaldehyde (starting material for the synthesis of 7) allowing the grafting of all types of alkoxy side chains is also reported. Bulk state properties of the four polymeric materials have been analyzed using various experimental methods giving information on the thermal behavior as well as self-assembling morphologies at different size scales. Crystalline superstructures of either spherulitic or rodlike morphology, comprised of polymeric backbone layers separated by the side chains are identified to develop by nucleation and growth process for symmetrically alkoxy substituted 15a-c. Discrepancy between optical (E-g(opt)) and electrochemical (E-g(ee)) band gaps was observed to be dependent on the bulkiness (15c) and length (15b) of the grafted side chains. Octadecyloxy side chains in 15b not only lead to well structured photoluminescence and electroluminescence spectra and higher fluorescence quantum yields but also allow the design of LED-devices of the configuration ITO/PEDOT/polymer/Ca with improved parameters (eta(ext) = 2.15%, luminance = 5760 cd/m(2)) relative to the octyloxy-substituted polymer 15a (eta(ext) = 0.79%, luminance = 1406 cd/m(2)). Despite the differences in the conjugation pattern between polymers 15 and polymers 17 [(-Ph-CdropC-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-)], an identical chromophore system of structure Ph-CdropC-Ph-CH=CH-Ph-CH=CH-Ph-CdropC-Ph was found to be responsible for their emissive behavior as confirmed by fluorescence kinetics measurements (tau, k(f), k(nr)) and quantum chemical calculations. The differences observed in their solid-state photophysical properties are ascribed to the combined effects of the backbone rigidity (as a function of the number of -CdropC- moieties in the repeating unit) and the nature of the side chains. Moreover less -CdropC- units within polymers 15 lead to the more than 100-fold improvement of their electroluminescent parameters compared to polymers 17.

  DOI：

  10.1021/ma0488111

文献信息

• Investigation of the Photophysical and Electrochemical Properties of Alkoxy-Substituted Arylene−Ethynylene/Arylene−Vinylene Hybrid Polymers
  作者：Daniel Ayuk Mbi Egbe、Bader Cornelia、Jürgen Nowotny、Wolfgang Günther、Elisabeth Klemm

  DOI：10.1021/ma0301395

  日期：2003.7.1

  High-molecular-weight, soluble and thermostable alkoxy-substituted arylene-ethynylene/ arylene-vinylene conjugated polymers, 13 and 14, have been successfully synthesized through the Horner-Wadsworth-Emmons olefination of luminophoric dialdehydes 7 and 9 and bisphosphonate 12 in very good yields. They were characterized through H-1 NMR, C-13 NMR, IR, and elemental analysis. The investigation of their photophysical and electrochemical properties has been carried out. Although almost identical absorption and emission spectra were obtained in dilute chloroform solution for all polymers 13, the full width at half-maximum (fwhm) value of the emission curves depends on the length of the attached side chains. The presence of anthracenylene units in 14 leads to a red shift of its absorption and emission spectra relative to 13. Strong self-reabsorption after excitation in solution was observed for this polymer. The solid-state photophysical properties of 13 and 14 (photoconductivity, absorption and emission spectra, fluorescence quantum yield, Stokes shift, and fwhm) greatly depend on the nature (linear or branched), length, and location of the grafted alkoxy side groups. Photoconductivity is easily detected in polymers having octadecyloxy chains (13aa, 13ab, 14). Long linear (octadecyl, i.e., 13aa) or short branched (2-ethylhexyl, i.e., 13cc) side chains at position R-2 (phenylene-vinylene segment) are necessary to obtain sharp and well-resolved emission spectra accompanied by high fluorescence quantum yields. The quasi-donor (phenylene-vinylene segment)-acceptor (arylene-ethynylene segment) nature of these polymers could explain the great discrepancy between the electrochemical band gap energy, E-g(ec) approximate to 1.60 eV, as obtained from the onset values of the redox potentials in cyclic voltammetry and in differential pulse polarography measurements, and the optical band gap energy, E-g(opt) approximate to 2.30 eV, from the absorption spectra.
• Supramolecular Ordering, Thermal Behavior, and Photophysical, Electrochemical, and Electroluminescent Properties of Alkoxy-Substituted Yne-Containing Poly(phenylene−vinylene)s
  作者：Daniel Ayuk Mbi Egbe、Benjamin Carbonnier、Liming Ding、David Mühlbacher、Eckhard Birckner、Tadeusz Pakula、Frank E. Karasz、Ulrich-Walter Grummt

  DOI：10.1021/ma0488111

  日期：2004.10.1

  Alkoxy-substituted and defect-free yne-containing poly(phenylene-vinylene)s, 15a-d, having the general constitutional unit (-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-) synthesized through the olefination reactions of the fluorophoric dialdehyde 7 [1,2-bis(4-formyl-2,5-dialkoxyphenyl)acetylene] with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 14a-d, are reported. A new synthetic route to 1-bromo-2,5-dialkoxybenzaldehyde (starting material for the synthesis of 7) allowing the grafting of all types of alkoxy side chains is also reported. Bulk state properties of the four polymeric materials have been analyzed using various experimental methods giving information on the thermal behavior as well as self-assembling morphologies at different size scales. Crystalline superstructures of either spherulitic or rodlike morphology, comprised of polymeric backbone layers separated by the side chains are identified to develop by nucleation and growth process for symmetrically alkoxy substituted 15a-c. Discrepancy between optical (E-g(opt)) and electrochemical (E-g(ee)) band gaps was observed to be dependent on the bulkiness (15c) and length (15b) of the grafted side chains. Octadecyloxy side chains in 15b not only lead to well structured photoluminescence and electroluminescence spectra and higher fluorescence quantum yields but also allow the design of LED-devices of the configuration ITO/PEDOT/polymer/Ca with improved parameters (eta(ext) = 2.15%, luminance = 5760 cd/m(2)) relative to the octyloxy-substituted polymer 15a (eta(ext) = 0.79%, luminance = 1406 cd/m(2)). Despite the differences in the conjugation pattern between polymers 15 and polymers 17 [(-Ph-CdropC-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-)], an identical chromophore system of structure Ph-CdropC-Ph-CH=CH-Ph-CH=CH-Ph-CdropC-Ph was found to be responsible for their emissive behavior as confirmed by fluorescence kinetics measurements (tau, k(f), k(nr)) and quantum chemical calculations. The differences observed in their solid-state photophysical properties are ascribed to the combined effects of the backbone rigidity (as a function of the number of -CdropC- moieties in the repeating unit) and the nature of the side chains. Moreover less -CdropC- units within polymers 15 lead to the more than 100-fold improvement of their electroluminescent parameters compared to polymers 17.