4,4-dicarboxylato-2,2'-bipyridine(2-) | 6813-38-3

• 物质功能分类: 医药中间体 - 杂环化合物 - 吡啶类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4,4-dicarboxylato-2,2'-bipyridine(2-)
• 英文别名: dcbpy2-；[2,2'-Bipyridine]-4,4'-dicarboxylate；2-(4-carboxylatopyridin-2-yl)pyridine-4-carboxylate
• CAS: 6813-38-3
• 化学式: C₁₂H₆N₂O₄
• 分子量: 242.191
• InChiKey: FXPLCAKVOYHAJA-UHFFFAOYSA-L

物化性质

• 熔点：
  >310°C
• 沸点：
  387.12°C (rough estimate)
• 密度：
  1.3468 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 安全说明：
  S26,S36,S37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  2933399090
• 危险品运输编号：
  NONH for all modes of transport
• 危险标志：
  GHS07
• 危险性描述：
  H315,H319,H335
• 危险性防范说明：
  P261,P305 + P351 + P338

制备方法与用途

2,2'-联吡啶-4,4'-二甲酸主要用于医药和生物化工领域。作为一种羧酸类衍生物，它可作为医药中间体使用。此外，该化合物还可用作敏化染料的配体材料。

反应信息

• 作为反应物：
  描述：

  [Ru(biq)₂Cl₂] 、 hexafluorophosphoric acid 、 4,4-dicarboxylato-2,2'-bipyridine(2-) 以 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 [Ru(bq)2(4,4'-dicarboxy-2,2'-bipyridine)](PF6)2
  参考文献：
  名称：

  Toward Exceeding the Shockley−Queisser Limit:  Photoinduced Interfacial Charge Transfer Processes that Store Energy in Excess of the Equilibrated Excited State

  摘要：

  Nanocrystalline (anatase), mesoporous TiO2 thin films were functionalized with [Ru(bpy)(2)(deebq)](PF6)(2), [Ru(bq)(2)(deeb)](PF6)(2), [Ru(deebq)(2)(bpy)](PF6)(2), [Ru(bpy)(deebq)(NCS)(2)], or [Os(bpy)(2)(deebq)](PF6)(2), where bpy is 2,2'-bipyridine, bq is 2,2'-biquinoline, and deeb and deebq are 4,4'-diethylester derivatives. These compounds bind to the nanocrystalline TiO2 films in their carboxylate forms with limiting surface coverages of 8 (+/- 2) x 10(-8) mol/cm(2). Electrochemical measurements show that the first reduction of these compounds (-0.70 V vs SCE) occurs prior to TiO2 reduction. Steady state illumination in the presence of the sacrificial electron donor triethylamine leads to the appearance of the reduced sensitizer. The thermally equilibrated metal-to-ligand charge-transfer excited state and the reduced form of these compounds do not inject electrons into TiO2. Nanosecond transient absorption measurements demonstrate the formation of an extremely long-lived charge separated state based on equal concentrations of the reduced and oxidized compounds. The results are consistent with a mechanism of ultrafast excited-state injection into TiO2 followed by interfacial electron transfer to a ground-state compound. The quantum yield for this process was found to increase with excitation energy, a behavior attributed to stronger overlap between the excited sensitizer and the semiconductor acceptor states. For example, the quantum yields for [Os(bpy)(2)(dcbq)]/TiO2 were phi(417 nm) = 0.18 +/- 0.02, phi(532.5 nm) = 0.08 +/- 0.02, and phi(683 nm) = 0.05 +/- 0.01. Electron transfer to yield ground-state products occurs by lateral intermolecular charge transfer. The driving force for charge recombination was in excess of that stored in the photoluminescent excited state. Chronoabsorption measurements indicate that ligand-based intermolecular electron transfer was an order of magnitude faster than metal-centered intermolecular hole transfer. Charge recombination was quantified with the Kohlrausch-Williams-Watts model.

  DOI：

  10.1021/ja060470e

文献信息

• Toward Exceeding the Shockley−Queisser Limit:  Photoinduced Interfacial Charge Transfer Processes that Store Energy in Excess of the Equilibrated Excited State
  作者：Paul G. Hoertz、Aaron Staniszewski、Andras Marton、Gerard T. Higgins、Christopher D. Incarvito、Arnold L. Rheingold、Gerald J. Meyer

  DOI：10.1021/ja060470e

  日期：2006.6.1

  Nanocrystalline (anatase), mesoporous TiO2 thin films were functionalized with [Ru(bpy)(2)(deebq)](PF6)(2), [Ru(bq)(2)(deeb)](PF6)(2), [Ru(deebq)(2)(bpy)](PF6)(2), [Ru(bpy)(deebq)(NCS)(2)], or [Os(bpy)(2)(deebq)](PF6)(2), where bpy is 2,2'-bipyridine, bq is 2,2'-biquinoline, and deeb and deebq are 4,4'-diethylester derivatives. These compounds bind to the nanocrystalline TiO2 films in their carboxylate forms with limiting surface coverages of 8 (+/- 2) x 10(-8) mol/cm(2). Electrochemical measurements show that the first reduction of these compounds (-0.70 V vs SCE) occurs prior to TiO2 reduction. Steady state illumination in the presence of the sacrificial electron donor triethylamine leads to the appearance of the reduced sensitizer. The thermally equilibrated metal-to-ligand charge-transfer excited state and the reduced form of these compounds do not inject electrons into TiO2. Nanosecond transient absorption measurements demonstrate the formation of an extremely long-lived charge separated state based on equal concentrations of the reduced and oxidized compounds. The results are consistent with a mechanism of ultrafast excited-state injection into TiO2 followed by interfacial electron transfer to a ground-state compound. The quantum yield for this process was found to increase with excitation energy, a behavior attributed to stronger overlap between the excited sensitizer and the semiconductor acceptor states. For example, the quantum yields for [Os(bpy)(2)(dcbq)]/TiO2 were phi(417 nm) = 0.18 +/- 0.02, phi(532.5 nm) = 0.08 +/- 0.02, and phi(683 nm) = 0.05 +/- 0.01. Electron transfer to yield ground-state products occurs by lateral intermolecular charge transfer. The driving force for charge recombination was in excess of that stored in the photoluminescent excited state. Chronoabsorption measurements indicate that ligand-based intermolecular electron transfer was an order of magnitude faster than metal-centered intermolecular hole transfer. Charge recombination was quantified with the Kohlrausch-Williams-Watts model.