1-(2-pyridylazo)-2-phenanthrol | 50722-39-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1-(2-pyridylazo)-2-phenanthrol
• 英文别名: 10-[2-(Pyridin-2-yl)hydrazinylidene]phenanthren-9(10H)-one；10-(pyridin-2-yldiazenyl)phenanthren-9-ol
• CAS: 50722-39-9
• 化学式: C₁₉H₁₃N₃O
• 分子量: 299.332
• InChiKey: RDNMATWQNUMOTQ-UHFFFAOYSA-N

物化性质

• 沸点：
  555.1±30.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  57.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(2-pyridylazo)-2-phenanthrol 、 manganese (II) acetate tetrahydrate 以 甲醇 、 氯仿 为溶剂， 反应 1.0h， 以40%的产率得到[Mn(1-(2-pyridylazo)-2-phenanthrolate)2]
  参考文献：
  名称：

  Molecular and Electronic Structures of Complexes Containing 1-(2-pyridylazo)-2-phenanthrol (PAPL): Revisiting a Redox-Active Ligand

  摘要：

  Herein we report the molecular structures and electronic properties of neutral, homoleptic, six-coordinate complexes of the general formula M(PAPL)(2), where PAPL is the monoanion of 1-(2-pyridylazo)-2-phenanthrol (M = Mn, Ni, Zn). Although, the coordination chemistry of PAPL has been investigated in a few previous reports in the 1970s and 1980s, there are, to our knowledge, no reported single crystal X-ray diffraction studies of any complexes, or any other electronic property or computational studies of complexes containing the PAPL anion until now. The electronic structures of the complexes are probed with a combination of cyclic voltammetry, UV-vis spectroscopy, and spectroelectrochemical measurements. Density functional theory calculations support the redox-active nature of the PAPL ligand. In all complexes we observe two reversible ligand-centered reduction processes, suggesting it may be possible to access the open-shell radical-anionic state of the ligand.

  DOI：

  10.1021/ic401618u
• 作为产物：
  描述：

  2-肼吡啶 、 菲醌 以 溶剂黄146 为溶剂， 反应 1.5h， 以70%的产率得到1-(2-pyridylazo)-2-phenanthrol
  参考文献：
  名称：

  Molecular and Electronic Structures of Complexes Containing 1-(2-pyridylazo)-2-phenanthrol (PAPL): Revisiting a Redox-Active Ligand

  摘要：

  Herein we report the molecular structures and electronic properties of neutral, homoleptic, six-coordinate complexes of the general formula M(PAPL)(2), where PAPL is the monoanion of 1-(2-pyridylazo)-2-phenanthrol (M = Mn, Ni, Zn). Although, the coordination chemistry of PAPL has been investigated in a few previous reports in the 1970s and 1980s, there are, to our knowledge, no reported single crystal X-ray diffraction studies of any complexes, or any other electronic property or computational studies of complexes containing the PAPL anion until now. The electronic structures of the complexes are probed with a combination of cyclic voltammetry, UV-vis spectroscopy, and spectroelectrochemical measurements. Density functional theory calculations support the redox-active nature of the PAPL ligand. In all complexes we observe two reversible ligand-centered reduction processes, suggesting it may be possible to access the open-shell radical-anionic state of the ligand.

  DOI：

  10.1021/ic401618u

文献信息

• Bivalent Cobalt Complexes with 1-(2-Pyridylazo)-2-naphthol and Analogous Ligands
  作者：Katsura Mochizuki、Masatoshi Fujimoto

  DOI：10.1246/bcsj.58.1520

  日期：1985.5

  Bivalent cobalt complexes with the title ligands were synthesized, isolated, and characterized by absorption spectra and magnetic moments. It has been suggested that the cobalt(II) complexes have more flexible structures than the corresponding cobalt(III) complexes. The cobalt(II) complexes were found to be oxidized to the cobalt(III) complexes in DMSO in the presence of copper(II) ions. Cyclic voltammetry

  与标题配体的二价钴配合物被合成、分离并通过吸收光谱和磁矩表征。有人提出，钴 (II) 配合物比相应的钴 (III) 配合物具有更灵活的结构。发现钴 (II) 配合物在铜 (II) 离子存在下在 DMSO 中被氧化成钴 (III) 配合物。循环伏安法阐明了乙腈中钴配合物的可逆 CoII/CoIII 对。发现 CoII/CoIII 对的 E1⁄2 值取决于配位体。讨论了E1⁄2与配体中邻羟基的pKa之间的关系。
• Spin-crossover in a homoleptic cobalt(<scp>ii</scp>) complex containing a redox-active NNO ligand
  作者：R. A. Taylor、A. J. Lough、M. T. Lemaire

  DOI：10.1039/c5tc03137k

  日期：——

  We report the preparation of a divalent cobalt complex containing the ligand 1-(2-pyridylazo)-2-phenanthrol (papl). The complex is neutral and homoleptic containg two equivalents of the anion of papl. Variable temperature magnetic susceptibility measurements indicate a gradual spin-crossover between the S = 1/2 and S = 3/2 states of the complex. This is corroborated by single crystal X-ray diffraction

  我们报告了包含配体1-（2-吡啶基偶氮）-2-菲咯啉（papl）的二价钴配合物的制备。该络合物是中性的，并且均含有两个当量的pap 1阴离子。可变温度磁化率测量结果表明，复合物的S = 1/2和S = 3/2状态之间有一个逐渐的自旋交叉。这在147和325 K的单晶X射线衍射实验中得到了证实，这些实验揭示了配位键距的差异与其他钴中观察到的自旋交叉相一致（II）复合体。该配合物具有氧化还原活性，并具有强烈​​的，以配体为中心的可见吸收带，该吸收带在醇溶剂（甲醇，乙醇）中已完全改变，表明在这些极性，质子溶剂中该配合物被氧化成钴（III）。
• Structure and magnetic properties of a cobalt(III) complex with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)
  作者：Natasha Van Damme、Vasyl Zaliskyy、Alan J. Lough、Martin T. Lemaire

  DOI：10.1016/j.poly.2015.01.014

  日期：2015.3

  variable temperature magnetic properties of a cobalt complex with the redox active ligand 1-(2-pyridylazo)-2-phenanthrol (papl). We observe production of an ionic complex consisting of cobalt(III) coordinated to two papl anions, with charge balance provided by a tetrahedral complex of cobalt(II) containing chlorides and THF solvent. The electronic spectra of this complex differs from that observed from

  我们报告了具有氧化还原活性配体1-（2-吡啶基偶氮）-2-菲咯啉（papl）的钴配合物的结构和可变温度磁性能。我们观察到由钴（III）配位到两个pap阴离子组成的离子配合物的产生，电荷平衡由钴（II）的四氯化物配合物提供，其中四价配合物含有氯化物和THF溶剂。该配合物的电子光谱与其他M（papl）2的电子光谱不同由于配体到金属的电荷转移（LMCT）状态做出了贡献，因此未在其他报道的二价金属配合物的光谱中观察到这种配合物。可变温度磁化率数据对于四面体配位的钴（II）离子而言是典型的，其数据来自轨道简并激发态和零场分裂。这项研究代表了首个具有三价金属离子的papl结构特征的金属配合物。我们还研究了配合物的电子和磁性，并用密度泛函理论计算来支持我们的结果。
• Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)
  作者：Robin A. Taylor、Alan J. Lough、Takele Seda、Prashanth K. Poddutoori、Martin T. Lemaire

  DOI：10.1016/j.poly.2016.11.044

  日期：2017.2

  The synthesis and study of redox-active ligand complexes has received much recent attention. We have recently explored the coordination chemistry of arylazo redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl) and herein expand the series of complexes to the Group 8 transition metal ion, iron. We report the preparation and structure of a divalent iron complex with the pap! anion, Fe(pap1)(2), which is diamagnetic and features ligand centered redox activity and intense visible electronic transitions. Three polymorphs of the Fe(papl)(2) complex are reported, including one that exhibits a structural phase transition at low temperature. Oxidation of Fe(papl)(2) with molecular iodine has produced the low-spin trivalent complex [Fe3+(papl)(2)](+) as an ionic complex with the I-3 anion. Density functional theory (dft) calculations and data from variable temperature Mossbauer spectroscopy experiments are provided to shed light on the electronic structures of these iron complexes. (C) 2016 Elsevier Ltd. All rights reserved.
• Bhoon, Y. K.; Pandeya, K. B.; Singh, R. P., 1979, p. 104 - 107
  作者：Bhoon, Y. K.、Pandeya, K. B.、Singh, R. P.

  DOI：——

  日期：——