5-(4-[2,2']Bipyridinyl-4-ylethynyl-phenylethynyl)-isophthalic acid dimethyl ester | 797761-32-1

• 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-[2,2']Bipyridinyl-4-ylethynyl-phenylethynyl)-isophthalic acid dimethyl ester
• 英文别名: Dimethyl 5-[2-[4-[2-(2-pyridin-2-ylpyridin-4-yl)ethynyl]phenyl]ethynyl]benzene-1,3-dicarboxylate；dimethyl 5-[2-[4-[2-(2-pyridin-2-ylpyridin-4-yl)ethynyl]phenyl]ethynyl]benzene-1,3-dicarboxylate
• CAS: 797761-32-1
• 化学式: C₃₀H₂₀N₂O₄
• 分子量: 472.5
• InChiKey: JZDJJMBCYDSVCT-UHFFFAOYSA-N

物化性质

• 沸点：
  687.7±55.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  78.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-(4-[2,2']Bipyridinyl-4-ylethynyl-phenylethynyl)-isophthalic acid dimethyl ester 、 sodium hexaflorophosphate 、 顺-双(2,2-二吡啶)二氯化钌(II) 水合物 以 四氢呋喃 、 乙醇 为溶剂， 以74%的产率得到ROD2-bpyRu(bpy)2(PF6)2
  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：

  Dimethyl 5-[2-[4-(2-trimethylsilylethynyl)phenyl]ethynyl]benzene-1,3-dicarboxylate 在 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-[2,2']Bipyridinyl-4-ylethynyl-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

文献信息

• Distance Dependent Electron Transfer at TiO₂ Interfaces Sensitized with Phenylene Ethynylene Bridged Ru^II–Isothiocyanate Compounds
  作者：Patrik G. Johansson、Andrew Kopecky、Elena Galoppini、Gerald J. Meyer

  DOI：10.1021/ja402193f

  日期：2013.6.5

  that were unaffected by temperature, irradiance, or the bridge units present on the molecular sensitizer were attributed to electron tunneling between TiO2 acceptor states. The photocurrent efficiencies of solar cells based on these compounds decreased markedly when the bridge units were present on the sensitizer. Iodine was found to form adducts with all three compounds, K = 1.8 ± 0.2 × 10(4) M(-1), but

  半导体纳米微晶中存在的过量电子会产生显着的电场，但该电场在分子电荷转移过程中所起的作用仍知之甚少。三个钌联吡啶基顺式-Ru(bpy)(LL)(NCS)2 化合物，其中 LL 是一个 4-取代的 bpy，具有零、一个或两个亚苯基乙炔桥单元，被锚定在介孔纳米晶 TiO2 薄膜上以具体量化界面电荷转移与发色团被设计成设置在离表面的可变距离处。将电子注入 TiO2 导致金属到配体的电荷转移吸收发生蓝移，这与潜在的斯塔克效应一致。电吸收数据用于量化化合物所经历的电场，该电场从 0.85 降至 0。22 MV/cm 随着 OPE 间隔物的数量从 0 增加到 2。 10(-8)-10(-5) s 时间尺度上的电荷复合与电场强度相关，具有明显的衰减因子 β = 0.12 Å(-1)。在 10(-4)-10(-1) s 时间尺度上观察到的电荷重组缓慢成分不受温度、辐照度或分子敏化剂上存在的桥单元的影响，这归因于