4,4’,6,6’-tetracarboxy-2,2’-bipyridine | 1127385-14-1

• 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’,6,6’-tetracarboxy-2,2’-bipyridine
• 英文别名: 4,4',6,6'-Bipyridine tetracarboxylic acid；6-(4,6-dicarboxypyridin-2-yl)pyridine-2,4-dicarboxylic acid
• CAS: 1127385-14-1
• 化学式: C₁₄H₈N₂O₈
• 分子量: 332.226
• InChiKey: KSVSUDAVLCEDJU-UHFFFAOYSA-N

物化性质

• 沸点：
  946.6±65.0 °C(Predicted)
• 密度：
  1.736±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  175
• 氢给体数：
  4
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  4,4’,6,6’-tetracarboxy-2,2’-bipyridine 在 硝酸 作用下， 以 水 为溶剂， 生成 2,2'-联吡啶
  参考文献：
  名称：

  Acid directed in situ oxidation and decarboxylation of 4,4′,6,6′-tetra-methyl-2,2′-bipyridine: Synthesis and structural characterisation of 4,4′,6-tri-carboxy-2,2′-bipyridine and its copper(II) coordination polymer

  摘要：

  The reaction of either 4,4',6,6'-tetramethyl-2,2'-bipyridine, L, or 4,4',6,6'-tetracarboxy-2,2'-bipyridine, H4L, with Cu(OAc)(2)center dot H2O under acidic hydrothermal conditions (50:1 H2O/HNO3; 160 degrees C) led to the formation of crystalline {[Cu(HL')(H2O)]center dot H2O}, 1, which was structurally characterised to identify H3L' as 4,4',6-tricarboxy-2,2'-bipyridine. Clearly, in situ mono-decarboxylation of a tetracarboxylic acid ligand gave the tricarboxy-analogue, H3L'. The structure of 1 consists of a 1D coordination polymer that cross-links through hydrogen-bonding between adjacent carboxylic acid and carboxylate groups, as well as through an aqua ligand and lattice water molecule, to form a densely interconnected 3D network. Regioselective mono-decarboxylation of L or H4L at the 6'-carboxylic acid position may also be affected by heating L or H4L in acidic solution under hydrothermal conditions (2:1 H2O/HNO3; 160 degrees C) to yield crystalline 4,4',6'-tricarboxy-2,2'-bipyridinium nitrate hydrate {[H4L'][NO3]center dot H2O}, 2, which was also structural characterised. The structure of 2 features an array of hydrogen-bonding interactions that generate a 3D network. More forceful heating of the acidic solution at 180 degrees C led to double decarboxylation and the formation of 4,4'-dicarboxy-2,2'-bipyridine, whereas heating at 200 degrees C led to total decarboxylation and the formation of 2,2'-bipyridine. Details of the structures of 1 and 2 along with their synthesis are discussed. (C) 2012 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2012.12.033
• 作为产物：
  描述：

  2,4-二甲基吡啶 在 potassium permanganate 、 palladium 10% on activated carbon 、 sodium hydroxide 作用下， 以 水 、 甲苯 、 叔丁醇 为溶剂， 反应 265.0h， 生成 4,4’,6,6’-tetracarboxy-2,2’-bipyridine
  参考文献：
  名称：

  用于从废水中去除高铼酸盐的超稳定锆基阳离子金属-有机框架

  摘要：

  从核废水中有效去除放射性99 TcO 4 -阴离子仍然是一个非常困难的未解决的问题。需要具有高稳定性、阴离子交换能力、优良选择性和可回收性的功能性吸附材料来解决这一问题。在这项工作中，我们设计了两种稳定的阳离子金属-有机骨架 (MOF)——Zr-tcbp-Me 和 Zr-tcpp-Me——可能用作吸附材料以去除99 TcO 4 –. 两种化合物均通过四羧酸配体与锆盐的溶剂热反应合成，然后进行合成后修饰（N-甲基化）。两种锆基 MOF 的结晶度在恶劣条件下都能很好地保持，并且它们对 ReO 4 -阴离子（一种99 TcO 4 -的非放射性类似物）表现出高吸附能力和选择性。Zr-tcbp-Me 和 Zr-tcpp-Me 在所有先前报道的阳离子 MOF 中表现出对酸度的最高框架稳定性，这些阳离子 MOF 已经过从废水中去除高铼酸盐的测试。

  DOI：

  10.1021/acs.inorgchem.1c00512

文献信息

• Substituted [Cu(i)(POP)(bipyridyl)] and related complexes: Synthesis, structure, properties and applications to dye-sensitised solar cells
  作者：Charlotte L. Linfoot、Patricia Richardson、Tracy E. Hewat、Omar Moudam、Michael M. Forde、Anna Collins、Fraser White、Neil Robertson

  DOI：10.1039/c0dt00190b

  日期：——

  The synthesis and subsequent spectroscopic, electrochemical, photophysical and computational characterisation of a series of heteroleptic Cu(I) complexes of general formula: [CuPOP4,4′(R)-bipyridyl}][BF4] and [CuPOP4,4′,6,6′(R)-bipyridyl}][BF4] is described (POP = bis2-(diphenylphosphanyl)phenyl} ether; R = Me, CO2H, CO2Et. The steric constraint imposed by the POP ligand can impede distortion towards

  一系列杂合剂的合成及随后的光谱，电化学，光物理和计算表征 铜（I）通式的配合物：[CuPOP 4，4 '（R） -联吡啶基}] [BF 4 ]和[CuPOP 4，4 '，6，6 '（R） -联吡啶基}] [BF 4 ]中描述了（流行音乐 = 双2-（二苯基膦烷基）苯基}醚; R = Me，CO 2 H，CO 2 Et。POP配体施加的空间位阻可阻止MLCT激发或氧化时向方形平面几何结构的畸变，这是在POP上不同取代基的背景下进行的。联吡啶配体。所获得的见识为功能设计开辟了新途径铜（I） 适用于光物理和光电化学应用的系统，例如用于染料敏化太阳能电池（DSSC）的敏化剂。
• Photochemical, Electrochemical, and Photoelectrochemical Water Oxidation Catalyzed by Water‐Soluble Mononuclear Ruthenium Complexes
  作者：Ting‐Ting Li、Wei‐Liang Zhao、Yong Chen、Fu‐Min Li、Chuan‐Jun Wang、Yong‐Hua Tian、Wen‐Fu Fu

  DOI：10.1002/chem.201403872

  日期：2014.10.20

  linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium‐tin‐oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding

  两种单核钌络合物[Ru（H 2 tcbp）（isoq）2 ]（1）和[Ru（H 2 tcbp）（pic）2 ]（2）（H 4 tcbp = 4,4'，6,6'-合成并充分表征了四羧基-2,2'-联吡啶，isoq =异喹啉，pic = 4-甲基吡啶。在4,4'-位置引入两个备用羧基，以增强1和2在水中的溶解度，并同时通过酯键将它们束缚到电极表面。的光化学，电化学，和光电化学水氧化性能1在中性水溶液中进行了研究。在电化学条件下，在沉积的铟锡氧化物阳极上进行水氧化，在1.42 V vs. NHE的条件下，电解10小时，在水氧化过程中，每个水氧化催化剂（WOC）1的转换数高于15,000 ，对应于周转频率为0.41 s -1。均相溶液中1的电化学水氧化的低超电势（0.17 V）可以通过使用[Ru（bpy）3 ] 2+（P1）（bpy = 2,2'-联吡啶）或[Ru （bpy）2（4,4′-（（COOEt）2
• A simple and environmentally benign synthesis of polypyridine-polycarboxylic acids
  作者：Niamh R. Kelly、Sandrine Goetz、Chris S. Hawes、Paul E. Kruger

  DOI：10.1016/j.tetlet.2010.12.074

  日期：2011.3

  An oxidation method using dilute nitric acid solutions under solvothermal conditions has been developed to synthesise a series of polypyridine-polycarboxylic acids. It has been successfully applied to a range of methyl substituted polypyridines including symmetrical and asymmetrical 2,2'-bipyridines; 2,2':6',2 ''-terpyridines and; 2,2':6',2 '':6 '',2'''-tetra-pyridines and yields crystalline polypyridine-polycarboxylic acids in a single step. Simple product recovery through filtration yields a recyclable filtrate. More forcing conditions led to demethylation of the polypyridine ligand most probably via decarboxylation. This simple approach avoids potentially harmful metal-based oxidants and negates any issues associated with the disposal of their resultant (hazardous) waste. (C) 2010 Elsevier Ltd. All rights reserved.
• Ultrastable Zirconium-Based Cationic Metal–Organic Frameworks for Perrhenate Removal from Wastewater
  作者：Guoyu Zhang、Kui Tan、Shikai Xian、Kai Xing、Hongbing Sun、Gene Hall、Liangying Li、Jing Li

  DOI：10.1021/acs.inorgchem.1c00512

  日期：2021.8.16

  effective removal of radioactive 99TcO4– anion from nuclear wastewater remains a very difficult unsolved problem. Functional adsorbent materials with high stability, anion-exchange capacity, excellent selectivity, and recyclability are much needed to solve this problem. In this work, we designed two stable cationic metal–organic frameworks (MOFs)—Zr-tcbp-Me and Zr-tcpp-Me—for possible use as adsorbent

  从核废水中有效去除放射性99 TcO 4 -阴离子仍然是一个非常困难的未解决的问题。需要具有高稳定性、阴离子交换能力、优良选择性和可回收性的功能性吸附材料来解决这一问题。在这项工作中，我们设计了两种稳定的阳离子金属-有机骨架 (MOF)——Zr-tcbp-Me 和 Zr-tcpp-Me——可能用作吸附材料以去除99 TcO 4 –. 两种化合物均通过四羧酸配体与锆盐的溶剂热反应合成，然后进行合成后修饰（N-甲基化）。两种锆基 MOF 的结晶度在恶劣条件下都能很好地保持，并且它们对 ReO 4 -阴离子（一种99 TcO 4 -的非放射性类似物）表现出高吸附能力和选择性。Zr-tcbp-Me 和 Zr-tcpp-Me 在所有先前报道的阳离子 MOF 中表现出对酸度的最高框架稳定性，这些阳离子 MOF 已经过从废水中去除高铼酸盐的测试。
• Acid directed in situ oxidation and decarboxylation of 4,4′,6,6′-tetra-methyl-2,2′-bipyridine: Synthesis and structural characterisation of 4,4′,6-tri-carboxy-2,2′-bipyridine and its copper(II) coordination polymer
  作者：Niamh R. Kelly、Sandrine Goetz、Chris S. Hawes、Paul E. Kruger

  DOI：10.1016/j.ica.2012.12.033

  日期：2013.7

  The reaction of either 4,4',6,6'-tetramethyl-2,2'-bipyridine, L, or 4,4',6,6'-tetracarboxy-2,2'-bipyridine, H4L, with Cu(OAc)(2)center dot H2O under acidic hydrothermal conditions (50:1 H2O/HNO3; 160 degrees C) led to the formation of crystalline [Cu(HL')(H2O)]center dot H2O}, 1, which was structurally characterised to identify H3L' as 4,4',6-tricarboxy-2,2'-bipyridine. Clearly, in situ mono-decarboxylation of a tetracarboxylic acid ligand gave the tricarboxy-analogue, H3L'. The structure of 1 consists of a 1D coordination polymer that cross-links through hydrogen-bonding between adjacent carboxylic acid and carboxylate groups, as well as through an aqua ligand and lattice water molecule, to form a densely interconnected 3D network. Regioselective mono-decarboxylation of L or H4L at the 6'-carboxylic acid position may also be affected by heating L or H4L in acidic solution under hydrothermal conditions (2:1 H2O/HNO3; 160 degrees C) to yield crystalline 4,4',6'-tricarboxy-2,2'-bipyridinium nitrate hydrate [H4L'][NO3]center dot H2O}, 2, which was also structural characterised. The structure of 2 features an array of hydrogen-bonding interactions that generate a 3D network. More forceful heating of the acidic solution at 180 degrees C led to double decarboxylation and the formation of 4,4'-dicarboxy-2,2'-bipyridine, whereas heating at 200 degrees C led to total decarboxylation and the formation of 2,2'-bipyridine. Details of the structures of 1 and 2 along with their synthesis are discussed. (C) 2012 Elsevier B. V. All rights reserved.