hydroxo(methoxo)(tetraphenylporphyrinato)antimony(V) | 177417-20-8

• 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: hydroxo(methoxo)(tetraphenylporphyrinato)antimony(V)
• CAS: 177417-20-8
• 化学式: C₄₅H₃₂N₄O₂Sb
• 分子量: 782.525
• InChiKey: XDDSATBKUZCEQV-NBICUONBSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [Sb(OMe)Br(tpp)]Br 在 OH^(1-) 作用下， 以 水 、 乙腈 为溶剂， 生成 hydroxo(methoxo)(tetraphenylporphyrinato)antimony(V)
  参考文献：
  名称：

  Inoue, Haruo; Okamoto, Takanobu; Kameo, Yohji, Journal of the Chemical Society. Perkin transactions I, 1994, # 1, p. 105 - 112

  摘要：

  DOI：

文献信息

• Effects of an Axial Amino Ligand on the Spectroscopic and Electrochemical Properties of Amino(methoxo)(tetraphenylporphyrinato)antimony(V) Complexes
  作者：Shin-ichiro Tsunami、Kousuke Tanaka、Jin Matsumoto、Tsutomu Shiragami、Masahide Yasuda

  DOI：10.1246/bcsj.81.583

  日期：2008.5.15

  We investigated the effects of an axial amino ligand on the spectroscopic and electrochemical properties of alkylamino(methoxo)(tetraphenylporphyrinato)antimony(V) bromide 1 and anilino(methoxo)(tetraphenylporphyrinato)antimony(V) bromide 2. Fluorescence measurements of 1 and 2 showed that their fluorescence quantum yields were lower than that of dihydroxo(tetraphenylporphyrinato)antimony(V) bromide (3) due to intramolecular electron transfer (ET) from the axial amino ligand to the excited porphyrin ring. Fluorescence was enhanced by the addition of a proton, which was caused by the protonation of the axial nitrogen atom, thereby preventing ET. From the titration curves of fluorescence quantum yield (Φf) versus proton concentration, we estimated the acid dissociation constants (pKa) for the conjugate acid of the axial amino ligand of 1 to be 4.41–5.03. The reduction potentials (E1⁄2red) of 2 depended strongly on the electronic effect of the p-substituents (X) on the axial aniline group whereas the E1⁄2red of methoxo(p-substituted-phenoxo)(tetraphenylporphyrinato)antimony(V) bromide was little affected by the p-substituents on the phenoxo ligand. These observations were interpreted as reflecting the participation of the axial amino ligand in the LUMO, calculated for 2 by the PM3 method.

  我们研究了轴向氨基配体对烷基氨基（甲氧基）（四苯基卟啉）锑(V)溴化物1和苯胺（甲氧基）（四苯基卟啉）锑(V)溴化物2的光谱和电化学性质的影响。对1和2的荧光测量显示，它们的荧光量子产率低于二羟基（四苯基卟啉）锑(V)溴化物（3），这是由于轴向氨基配体向激发的卟啉环发生了分子内电子转移（ET）。通过质子化轴向氮原子，添加质子增强了荧光，从而防止了电子转移。通过荧光量子产率（Φf）与质子浓度的滴定曲线，我们估计了1的轴向氨基配体的共轭酸的酸解离常数（pKa）为4.41–5.03。2的还原电位（E1⁄2red）强烈依赖于p位取代基（X）对轴向苯胺基团的电子效应，而甲氧基（p-取代苯氧基）（四苯基卟啉）锑(V)溴化物的E1⁄2red几乎不受苯氧配体上p位取代基的影响。这些观察结果被解释为反映了轴向氨基配体参与了通过PM3方法为2计算的LUMO。