4-fluoro-4-phenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene | 221159-18-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4-fluoro-4-phenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 5,11-Diethyl-2-fluoro-4,6,8,10,12-pentamethyl-2-phenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene；5,11-diethyl-2-fluoro-4,6,8,10,12-pentamethyl-2-phenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 221159-18-8
• 化学式: C₂₄H₃₀BFN₂
• 分子量: 376.325
• InChiKey: LBXZYVJEHPJKPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.29
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  溴苯 、 硼,[3-乙基-5-[1-(4-乙基-3,5-二甲基-2H-吡咯-2-亚基-kN)乙基]-2,4-二甲基-1H-吡咯酸根-kN]二氟-,(T-4)- 在 magnesium 作用下， 以 乙醚 为溶剂， 以40%的产率得到4-fluoro-4-phenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Synthesis and Photophysical Properties of Borondipyrromethene Dyes Bearing Aryl Substituents at the Boron Center

  摘要：

  Several borondipyrromethene (Bodipy) dyes bearing an aryl nucleus linked directly to the boron center have been prepared under mild conditions. The choice of Grignard or lithio organo-metallic reagents allows the isolation of B(F)(aryl) or B(aryl)(2) derivatives; where aryl refers to phenyl, anisyl, naphthyl, or pyrenyl fragments. A single crystal, X-ray structure determination for the bis-anisyl compound shows that the sp(3) hybridized boron center remains pseudo-tetrahedral and that the B-C bond distances are 1.615 and 1.636 angstrom. All compounds are electrode active but replacement of the fluorine atoms by aryl fragments renders the Bodipy unit more easily oxidized by 100 mV in the B(F)(aryl) and 180 mV in the B(aryl)(2) compounds whereas reduction is made more difficult by a comparable amount. Strong fluorescence is observed from the Bodipy fluorophore present in each of the new dyes, with the radiative rate constant being independent of the nature of the aryl substituent. The fluorescence quantum yields are solvent dependent and, at least in some cases (aryl = anisyl or pyrenyl), nonradiative decay from the first-excited singlet state is strongly activated. There is no indication, however, for population of a charge-transfer state, in which the aryl substituent acts as donor and the Bodipy fragment functions as acceptor, that is strongly coupled to the ground state. Instead, it is conjectured that nonradiative decay involves a conformational change driven by the solvophobic effect. Thus, the rate of nonradiative decay in any given solvent increases with increasing surface accessibility (or molar volume) of the aryl substituent. Intramolecular energy transfer from pyrene or naphthalene residues to Bodipy is quantitative.

  DOI：

  10.1021/ja062405a

文献信息

• New fluorescent aryl- or ethynylaryl-boron-substituted indacenes as promising dyes
  作者：Gilles Ulrich、Christine Goze、S?bastien Goeb、Pascal Retailleau、Raymond Ziessel

  DOI：10.1039/b604830g

  日期：——

  A generic design principle based on the use of organometallic (Li or Mg) reagents for the substitution of the fluoro ligands in difluoroboradiazaindacene is described. A library of compounds bearing various substituents (butyl, phenyl, naphthyl, pyrenyl, ethynylnaphthyl, ethynylfluorenyl, ethynylcarbazoyl, ethynylperylenyl, ethynylthiophenyl and ethynylterpyridinyl) has been prepared and characterized. Electrochemical and photochemical measurements show that these novel dyes remain redox-active and strongly luminescent. They offer an interesting perspective for applications in labelling and electroluminescence.

  描述了基于使用有机金属（Li 或 Mg）试剂取代二氟硼二氮茚中的氟配体的通用设计原理。已制备并表征了带有各种取代基（丁基、苯基、萘基、芘基、乙炔基萘基、乙炔基芴基、乙炔基咔唑酰基、乙炔基苝基、乙炔基苯硫基和乙炔基三联吡啶基）的化合物库。电化学和光化学测量表明，这些新型染料仍然具有氧化还原活性和强发光性。它们为标记和电致发光的应用提供了有趣的视角。
• Synthesis and Photophysical Properties of Borondipyrromethene Dyes Bearing Aryl Substituents at the Boron Center
  作者：Christine Goze、Gilles Ulrich、Laura J. Mallon、Ben D. Allen、Anthony Harriman、Raymond Ziessel

  DOI：10.1021/ja062405a

  日期：2006.8.1

  Several borondipyrromethene (Bodipy) dyes bearing an aryl nucleus linked directly to the boron center have been prepared under mild conditions. The choice of Grignard or lithio organo-metallic reagents allows the isolation of B(F)(aryl) or B(aryl)(2) derivatives; where aryl refers to phenyl, anisyl, naphthyl, or pyrenyl fragments. A single crystal, X-ray structure determination for the bis-anisyl compound shows that the sp(3) hybridized boron center remains pseudo-tetrahedral and that the B-C bond distances are 1.615 and 1.636 angstrom. All compounds are electrode active but replacement of the fluorine atoms by aryl fragments renders the Bodipy unit more easily oxidized by 100 mV in the B(F)(aryl) and 180 mV in the B(aryl)(2) compounds whereas reduction is made more difficult by a comparable amount. Strong fluorescence is observed from the Bodipy fluorophore present in each of the new dyes, with the radiative rate constant being independent of the nature of the aryl substituent. The fluorescence quantum yields are solvent dependent and, at least in some cases (aryl = anisyl or pyrenyl), nonradiative decay from the first-excited singlet state is strongly activated. There is no indication, however, for population of a charge-transfer state, in which the aryl substituent acts as donor and the Bodipy fragment functions as acceptor, that is strongly coupled to the ground state. Instead, it is conjectured that nonradiative decay involves a conformational change driven by the solvophobic effect. Thus, the rate of nonradiative decay in any given solvent increases with increasing surface accessibility (or molar volume) of the aryl substituent. Intramolecular energy transfer from pyrene or naphthalene residues to Bodipy is quantitative.