dimethyl 5-((4-ethynylphenyl)ethynyl)isophthalate | 797761-29-6

• 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: dimethyl 5-((4-ethynylphenyl)ethynyl)isophthalate
• 英文别名: dimethyl 5-[2-(4-ethynylphenyl)ethynyl]benzene-1,3-dicarboxylate
• CAS: 797761-29-6
• 化学式: C₂₀H₁₄O₄
• 分子量: 318.329
• InChiKey: WPOPZFWNOFYKIJ-UHFFFAOYSA-N

物化性质

• 沸点：
  479.1±45.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  dimethyl 5-((4-ethynylphenyl)ethynyl)isophthalate 在 四(三苯基膦)钯 哌啶 、 copper(l) iodide 、 四丁基氟化铵 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 生成 5-[4-(4-[2,2']Bipyridinyl-4-ylethynyl-phenylethynyl)-phenylethynyl]-isophthalic acid dimethyl ester
  参考文献：
  名称：

  Excited State Electron Transfer from Ru(II) Polypyridyl Complexes Anchored to Nanocrystalline TiO₂ through Rigid-Rod Linkers

  摘要：

  Rigid-rod linkers varying in length were used to bind Ru(II) polypyridyl complexes to the surface of TiO2 (anatase) and of ZrO2 nanoparticle thin films. The linkers were made of p-phenyleneethynylene (Ph-E), bridges carrying two COOR anchoring groups at the end and were capped with Ru(II) polypyridyl complexes as the sensitizing chromophores. Two series of rigid-rod sensitizers were prepared: Ru complexes having bpy or 4,4'-(Cl)(2)-bpy as the ancillary ligands. In the first series, the excited state was localized on the rigid-rod linker, in the second series, the excited states were localized on the 4,4'-(Cl)(2)-bpy ligands. The rigid-rod sensitizers with Ru(bpy)(2) complexes did bind strongly (K-ad similar to 10(5) M-1) with high surface coverages (similar to10(-8) mol/cm(2)) on the nanostructured metal oxide films, ZrO2 and anatase TiO2. The length of the fully conjugated rigid-rod linker influences the photophysical properties of the sensitizer, and nanosecond transient absorption measurements indicated long-lived metal-to-ligand charge-transfer (MLCT) excited states (similar to2 mus) with evidence for delocalization onto the rigid-rod linker. The interfacial electron transfer behavior on TiO2 was found to be dependent on the Bronsted acidity or basicity of the surface. On base pretreated TiO2, the excited state electron injection yields were low and could be increased by addition of LiClO4 to an external CH3CN solution. Under these conditions, a fraction of the injection process could be time resolved on a 10 ns time scale. On acidic TiO2, ultrafast excited state electron injection was observed for both series. Recombination was found to be second order with average rate constants independent of which rigid-rod sensitizer was excited. For rigid-rod sensitizers with Ru(4,4'-(Cl)(2)-bpy)(2), there was evidence for a direct interaction between the 4,4'(Cl)(2)-bpy ligands and the TiO2 surface. Photophysical and interfacial electron transfer properties of these Cl-substituted complexes were nearly independent of the rigid-rod length.

  DOI：

  10.1021/jp047454t
• 作为产物：
  描述：

  1,4-双[(三甲基硅基)乙炔基]苯 在 copper(l) iodide 、 四丁基氟化铵 、 甲基锂 、 三乙胺 、 三苯基膦 、 lithium bromide 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 dimethyl 5-((4-ethynylphenyl)ethynyl)isophthalate
  参考文献：
  名称：

  均一的“星状” Ru（II）聚吡啶基络合物：屏蔽的发色团，用于研究敏化剂-TiO 2界面上的电荷转移

  摘要：

  三个均质的星形钌聚吡啶基络合物，分别称为Star YZ1，Star YZ2和Star YZ3，其中Ru（II）中心与三个联吡啶配体配位，每个配体带有两个低聚（亚苯基乙炔基）（OPE）刚性连接单元，以间苯二甲酸终止合成用于结合至金属氧化物表面的酯基（Ipa）。在Star YZ3中，每个OPE接头均被两个正丁氧基（n- BuO）增溶基团取代。合成了具有均一性但缺乏八面体对称性的星形配合物YZ4作为参考化合物。使用两种方法合成Star配合物：在第一种方法中，Ru（4,4'-（Br）2 -2,2'-bpy）3在Sonogashira交叉偶联反应中与乙炔基-OPE-Ipa接头反应。在第二步中，使2,2'-bpy-OPE-Ipa配体与Ru（DMSO）4（PF 6）2反应。研究了Star配合物在溶液中的光物理行为，并将其固定在介孔纳米TiO 2薄膜（Star / TiO 2）的表面。初步近似，当将化合物固定在TiO

  DOI：

  10.1021/ic4004565

文献信息

• Excited State Electron Transfer from Ru(II) Polypyridyl Complexes Anchored to Nanocrystalline TiO₂ through Rigid-Rod Linkers
  作者：Dong Wang、Richard Mendelsohn、Elena Galoppini、Paul G. Hoertz、Rachael A. Carlisle、Gerald J. Meyer

  DOI：10.1021/jp047454t

  日期：2004.10.1

  Rigid-rod linkers varying in length were used to bind Ru(II) polypyridyl complexes to the surface of TiO2 (anatase) and of ZrO2 nanoparticle thin films. The linkers were made of p-phenyleneethynylene (Ph-E), bridges carrying two COOR anchoring groups at the end and were capped with Ru(II) polypyridyl complexes as the sensitizing chromophores. Two series of rigid-rod sensitizers were prepared: Ru complexes having bpy or 4,4'-(Cl)(2)-bpy as the ancillary ligands. In the first series, the excited state was localized on the rigid-rod linker, in the second series, the excited states were localized on the 4,4'-(Cl)(2)-bpy ligands. The rigid-rod sensitizers with Ru(bpy)(2) complexes did bind strongly (K-ad similar to 10(5) M-1) with high surface coverages (similar to10(-8) mol/cm(2)) on the nanostructured metal oxide films, ZrO2 and anatase TiO2. The length of the fully conjugated rigid-rod linker influences the photophysical properties of the sensitizer, and nanosecond transient absorption measurements indicated long-lived metal-to-ligand charge-transfer (MLCT) excited states (similar to2 mus) with evidence for delocalization onto the rigid-rod linker. The interfacial electron transfer behavior on TiO2 was found to be dependent on the Bronsted acidity or basicity of the surface. On base pretreated TiO2, the excited state electron injection yields were low and could be increased by addition of LiClO4 to an external CH3CN solution. Under these conditions, a fraction of the injection process could be time resolved on a 10 ns time scale. On acidic TiO2, ultrafast excited state electron injection was observed for both series. Recombination was found to be second order with average rate constants independent of which rigid-rod sensitizer was excited. For rigid-rod sensitizers with Ru(4,4'-(Cl)(2)-bpy)(2), there was evidence for a direct interaction between the 4,4'(Cl)(2)-bpy ligands and the TiO2 surface. Photophysical and interfacial electron transfer properties of these Cl-substituted complexes were nearly independent of the rigid-rod length.
• Homoleptic “Star” Ru(II) Polypyridyl Complexes: Shielded Chromophores to Study Charge-Transfer at the Sensitizer-TiO₂ Interface
  作者：Patrik G. Johansson、Yongyi Zhang、Gerald J. Meyer、Elena Galoppini

  DOI：10.1021/ic4004565

  日期：2013.7.15

  solubilizing groups. Star complex YZ4, which is homoleptic but lacks the octahedral symmetry, was synthesized as a reference compound. The Star complexes were synthesized using two approaches: in the first, Ru(4,4′-(Br)2-2,2′-bpy)3 was reacted in a Sonogashira cross coupling reaction with the ethynyl-OPE-Ipa linkers; in the second, the 2,2′-bpy-OPE-Ipa ligands were reacted with Ru(DMSO)4(PF6)2. The photophysical

  三个均质的星形钌聚吡啶基络合物，分别称为Star YZ1，Star YZ2和Star YZ3，其中Ru（II）中心与三个联吡啶配体配位，每个配体带有两个低聚（亚苯基乙炔基）（OPE）刚性连接单元，以间苯二甲酸终止合成用于结合至金属氧化物表面的酯基（Ipa）。在Star YZ3中，每个OPE接头均被两个正丁氧基（n- BuO）增溶基团取代。合成了具有均一性但缺乏八面体对称性的星形配合物YZ4作为参考化合物。使用两种方法合成Star配合物：在第一种方法中，Ru（4,4'-（Br）2 -2,2'-bpy）3在Sonogashira交叉偶联反应中与乙炔基-OPE-Ipa接头反应。在第二步中，使2,2'-bpy-OPE-Ipa配体与Ru（DMSO）4（PF 6）2反应。研究了Star配合物在溶液中的光物理行为，并将其固定在介孔纳米TiO 2薄膜（Star / TiO 2）的表面。初步近似，当将化合物固定在TiO