2,2-Difluoro-4,6,10,12-tetramethyl-5,8,11-triphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene | 1359876-86-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 2,2-Difluoro-4,6,10,12-tetramethyl-5,8,11-triphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• 英文别名: 2,2-difluoro-4,6,10,12-tetramethyl-5,8,11-triphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1359876-86-0
• 化学式: C₃₁H₂₇BF₂N₂
• 分子量: 476.377
• InChiKey: MMNPKKKCRPJHQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.73
• 重原子数：
  36
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,4-二甲基吡咯 在 四(三苯基膦)钯 、 碘 、 碘酸 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 2,2-Difluoro-4,6,10,12-tetramethyl-5,8,11-triphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
  参考文献：
  名称：

  利用BODIPY染料中的聚集诱导发射和扭曲的分子内电荷转移来选择性检测水性介质和活细胞中的氟化物

  摘要：

  利用Suzuki成功设计并合成了一种新的基于硼二吡咯亚甲基（BODIPY）的红色荧光探针，该探针由电子受体1,3,5,7-四甲基-8-苯基-BODIPY（BDP）和电子供体三苯胺（TPA）单元组成。交叉耦合方法TPA-BDP利用聚集诱导发射（AIE）和扭曲分子内电荷转移（TICT）的优势。TPA-BDP的X射线晶体结构揭示了C的网络H⋯F分子间相互作用，可有助于使分子构象刚性化。因此，聚集限制了与供体部分相关的分子内旋转，从而导致发射效率的极大提高。这种新型染料具有高灵敏度和对氟离子的出色选择性，在水性介质中的检出限为0.73μM。通过1 H NMR，19 F NMR，11 B NMR和质谱系统地研究了传感机理。建议氟化物在BDP核心发生亲核取代反应，从而破坏TPA-BDP的结构，从而导致TPA-BDP发出红色荧光。已淬灭。值得注意的是，TPA-BDP已用于细胞毒性非常低的活细胞中的荧光成像和氟离子检测。

  DOI：

  10.1016/j.jphotochem.2018.03.020

文献信息

• Geometry Relaxation-Induced Large Stokes Shift in Red-Emitting Borondipyrromethenes (BODIPY) and Applications in Fluorescent Thiol Probes
  作者：Yinghui Chen、Jianzhang Zhao、Huimin Guo、Lijuan Xie

  DOI：10.1021/jo202215x

  日期：2012.3.2

  2-Thienyl and 2,6-bisthienyl BODIPY derivatives (BS-SS and BS-DS) were prepared that show intense absorption (epsilon = 65000 M-1 cm(-1) at 507 nm) and a large Stokes shift (96 nm) vs the small Stokes shift of typical BODIPY (<15 nm). Control compounds with a thienyl unit at the 8-position or phenyl substituents at the 2,6-positions were prepared (BS-1 and 9). BS-1 shows absorption/emission in the blue-shifted range and a small Stokes shift (12 nm). Compound 9 shows absorption in the red-shifted range, but the Stokes shift (<30 nm) is much smaller than that for BS-SS and BS-DS. DFT calculations propose the large Stokes shifts of BS-SS and BS-DS are due to the remarkable geometry relaxation upon photoexcitation and its substantial effect on the energy levels of molecular orbitals. For the dyes with small Stokes shifts, much smaller geometry relaxations were found. The fluorophores were used for fluorescent thiol probes, with 2,4-dinitrobenzenesulfonyl (DNBS) as the fluorescence switch. Both fluorescence OFF-ON and unprecedented ON-OFF transduction were observed, which are attributed to the different photoinduced intramolecular electron-transfer (PET) profile. All the photophysics were rationalized by DFT calculations based on the concept of "electronic states" instead of the very often used approximation of "molecular orbitals".