3-(3-bromophenylazo)pyridine | 1360944-93-9

• 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: 3-(3-bromophenylazo)pyridine
• 英文别名: (3-Bromophenyl)-pyridin-3-yldiazene
• CAS: 1360944-93-9
• 化学式: C₁₁H₈BrN₃
• 分子量: 262.109
• InChiKey: UPPQMAMAHAQDOV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(3-bromophenylazo)pyridine 、 2-甲酰基苯硼酸 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 16.0h， 以95%的产率得到2-(3-phenylazopyridine)benzaldehyde
  参考文献：
  名称：

  用于结构和电子转换的单个偶氮吡啶取代的卟啉分子。

  摘要：

  合成了一种新型的偶氮吡啶官能化的镍卟啉作为模型化合物，用于沉积和在表面上转换。通过扫描隧道显微镜/光谱学发现了Au（111）上单分子的两个几何和电子不同状态，并通过密度泛函计算进行了分析。

  DOI：

  10.1039/c0cc00959h
• 作为产物：
  描述：

  m-bromophenylhydroxylamine 在 iron(III) chloride 作用下， 以 水 为溶剂， 反应 0.25h， 生成 3-(3-bromophenylazo)pyridine
  参考文献：
  名称：

  Photoswitchable Magnetic Resonance Imaging Contrast by Improved Light-Driven Coordination-Induced Spin State Switch

  摘要：

  We present a fully reversible and highly efficient on-off photoswitching of magnetic resonance imaging (MRI) contrast with green (500 nit), and violet-blue (435 nm) light. The contrast change is based on inframolecular light-driven coordination-induced spin state switch (LD-CISSS), performed with azopyridine-substituted Ni-porphyrins. The relaxation time Of the solvent protons in 3 mM solutions of the azoporphyrins in DMSO was switched between 3.5 and 1.7 s. The relaxivity of the contrast agent changes by a factor of 6.7. No fatigue or side reaction was observed, even after >100 000 switching cycles in air at room temperature. Electron-donating substituents at the pyridine improve the LD-CISSS in two ways: better photostationary states are achieved, and intramolecular binding is enhanced.

  DOI：

  10.1021/jacs.5b00929

文献信息

• Modular Synthetic Route to Monofunctionalized Porphyrin Architectures
  作者：Gernot Heitmann、Marcel Dommaschk、Roland Löw、Rainer Herges

  DOI：10.1021/acs.orglett.6b02507

  日期：2016.10.21

  porphyrin and its application as a versatile precursor for building up functional ortho-substituted tetraaryl porphyrin architectures is reported. This precursor porphyrin provides the basis for efficient modular syntheses of porphyrin compounds with covalently attached axial ligands which are important as enzyme model complexes, electron transfer dyads, and many other applications. In the present study

  报道了硼化的Ni 2+卟啉的合成及其作为建立功能性邻位取代的四芳基卟啉结构的通用前体的应用。该前体卟啉为有效合成具有卟啉化合物的化合物提供了基础，该化合物具有共价连接的轴向配体，这对于酶模型复合物，电子转移二元化合物和许多其他应用很重要。在本研究中，前体卟啉用于分子自旋开关的合成，该分子自旋开关先前显示出很高的潜力，可作为磁共振成像的光敏造影剂。
• Synthesis of Functionalized Perfluorinated Porphyrins for Improved Spin Switching
  作者：M. Dommaschk、C. Näther、R. Herges

  DOI：10.1021/acs.joc.5b01524

  日期：2015.9.4

  We have established a method to synthesize perfluorinated meso-phenylporphyrins with one phenyl group bearing a substituent in the ortho position. These novel electron-deficient porphyrins are interesting for model enzymes, catalysis, photodynamic therapy, and electron transfer. The key step is the synthesis of an iodine-substituted porphyrin and its Suzuki cross coupling with boronic acid derivatives. We applied the novel strategy to synthesize a highly electron-deficient, azopyridine-substituted Ni-porphyrin that undergoes an improved ligand-driven coordination-induced spin-state switch.
• Photoswitchable Magnetic Resonance Imaging Contrast by Improved Light-Driven Coordination-Induced Spin State Switch
  作者：Marcel Dommaschk、Morten Peters、Florian Gutzeit、Christian Schütt、Christian Näther、Frank D. Sönnichsen、Sanjay Tiwari、Christian Riedel、Susann Boretius、Rainer Herges

  DOI：10.1021/jacs.5b00929

  日期：2015.6.24

  We present a fully reversible and highly efficient on-off photoswitching of magnetic resonance imaging (MRI) contrast with green (500 nit), and violet-blue (435 nm) light. The contrast change is based on inframolecular light-driven coordination-induced spin state switch (LD-CISSS), performed with azopyridine-substituted Ni-porphyrins. The relaxation time Of the solvent protons in 3 mM solutions of the azoporphyrins in DMSO was switched between 3.5 and 1.7 s. The relaxivity of the contrast agent changes by a factor of 6.7. No fatigue or side reaction was observed, even after >100 000 switching cycles in air at room temperature. Electron-donating substituents at the pyridine improve the LD-CISSS in two ways: better photostationary states are achieved, and intramolecular binding is enhanced.
• Single azopyridine-substituted porphyrin molecules for configurational and electronic switching
  作者：Francesca Matino、Guillaume Schull、Umasish Jana、Felix Köhler、Richard Berndt、Rainer Herges

  DOI：10.1039/c0cc00959h

  日期：——

  A new azopyridine functionalized Ni-porphyrin was synthesized as a model compound for deposition and switch on surfaces. Two geometrically and electronically different states of single molecules on Au(111) were found by scanning tunneling microscopy/spectroscopy and analyzed with density functional calculations.

  合成了一种新型的偶氮吡啶官能化的镍卟啉作为模型化合物，用于沉积和在表面上转换。通过扫描隧道显微镜/光谱学发现了Au（111）上单分子的两个几何和电子不同状态，并通过密度泛函计算进行了分析。