tetrakis-strati-bis(5,10,15,20-tetraphenylporphyrin) | 138312-89-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: tetrakis-strati-bis(5,10,15,20-tetraphenylporphyrin)
• CAS: 138312-89-7
• 化学式: C₁₀₀H₇₆N₁₆O₄
• 分子量: 1565.81
• InChiKey: CWFHYSOZBDTNKE-XCPIWHJLSA-N

反应信息

• 作为产物：
  描述：

  C₁₀₈H₉₂N₁₆O₄ 在 ammonium hydroxide 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 生成 tetrakis-strati-bis(5,10,15,20-tetraphenylporphyrin)
  参考文献：
  名称：

  Symmetrical and unsymmetrical quadruply aza-bridged, closely interspaced, cofacial bis(5,10,15,20-tetraphenylporphyrin)s. 2. Synthesis, characterization, and conformational effects of solvents

  摘要：

  Several water- and non-water-soluble symmetrical and unsymmetrical quadruply aza bridged closely interspaced cofacial bis(5,10,15,20-tetraphenylporphyrin)s have been synthesized and fully characterized by 2D H-1-H-1 NMR (COSY), 2D C-13-H-1 NMR, FABMS, UV/vis, IR, and fluorescence spectral techniques. It was established, on the basis of H-1 NMR, UV/vis, and emission spectrophotometries, that tetrakis[m,m-(methylene(m-pyridinesulfonyl)imino)methylene]-strati-bis-(5,10,15,20-tetraphenylporphyrin) (5), tetrakis[m,m-(methylene(m-pyridiniumsulfonyl)imino)methylene]-strati-bis-(5,10,15,20-tetraphenylporphyrin) chloride (7), and tetrakis[m,m-(methylene(p-toluenesulfonyl)imino)methylene]-strati-bis(5,10,15,20-tetraphenylporphyrin) (11) exist in more than one conformation in DMSO and in only one symmetrical conformation in CHCl3. The biszinc and tetraprotonated 5, 7, and 11 exist in one conformation regardless of the solvent. These observations have been attributed to an interaction between DMSO and the pyrrolic N-H protons of the porphyrin cores which is inhibited by metalation (Zn2+) or protonation of the porphyrin moiety. Molecular dynamics calculations reveal that the intracavity interactions of 5 with DMSO are more important than the intercavity interactions which result in discrete, unsymmetrical conformations of the dimer. In contrast, tris[m,m-(methylene(m-pyridinesulfonyl)imino)methylene]-mono((((methylene-oxy)carbonyl)oxy)methylene-strati-bis(5,10,15,20-tetraphenylporphyrin) (6), tetrakis[m,m-(methylenecyanoimino)-methylene]-strati-bis(5,10,15,20-tetraphenylporphyrin) (8), tris[m,m-(methylenecyanoimino)methylene]-mono((((methyleneoxy)carbonyl)oxy)methylene)-strati-bis(5,10,15,20-tetraphenylporphyrin) (9), and tetrakis[m,m-(methylene(formamido)imino)methylene]-strati-bis(5,10,15,20-tetraphenylporphyrin) (10) do not show any conformational changes upon switching from chloroform to DMSO. This is attributed to the long interplanar distances calculated for the porphyrin dimers which prevent any intracavity coordination of DMSO with both porphyrin moieties. H-1 NMR variable-temperature experiments of porphyrin dimer 5 in DMSO show that the conformation of the dimer is greatly affected by temperature. While at room temperature 5 exists in more than one conformation, at higher temperatures (150-degrees-C) only one conformation is populated. It is proposed that at room temperature, the existence of a hydrogen-bonding network between DMSO and the dimer results in more than one conformation, while at higher temperatures the network is destroyed to furnish an average conformation.

  DOI：

  10.1021/ja00038a065