9-butyl-6-[4-(N,N-dimethylamino)]phenylethynyl-3-N-(4-fluoro)benzylaminomethylcarbazole | 1198605-15-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 9-butyl-6-[4-(N,N-dimethylamino)]phenylethynyl-3-N-(4-fluoro)benzylaminomethylcarbazole
• CAS: 1198605-15-0
• 化学式: C₃₄H₃₅N₃
• 分子量: 485.672
• InChiKey: YNHCZIQWKNWOIP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.35
• 重原子数：
  37.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  20.2
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  9-butyl-6-[4-(N,N-dimethylamino)]phenylethynyl-3-N-(4-fluoro)benzylaminomethylcarbazole 、 propane-1,3-diyl(o-(bromomethyl)phenyl)boronate 在 K₂CO₃ 作用下， 以 乙腈 为溶剂， 以21.3%的产率得到2-[[[(N-butyl-6-[4'-dimethylaminophenylethynyl]-9H-carbazol-3-yl)methyl]-[[phenylmethyl]amino]methyl]phenyl]boronic acid
  参考文献：
  名称：

  Rational Design of d-PeT Phenylethynylated-Carbazole Monoboronic Acid Fluorescent Sensors for the Selective Detection of α-Hydroxyl Carboxylic Acids and Monosaccharides

  摘要：

  We have synthesized three new phenylethynylated carbazole boronic acid sensors, which were predicted to display novel d-PeT fluorescence transduction (PeT, photoinduced electron transfer; fluorophore as the electron donor of the electron transfer, ET) by DFT/TDDFT calculations. The d-PeT effect is characterized by a lower background fluorescence at acidic pH than at neutral pH, which is in stark contrast to the normal a-PeT effect (fluorophore as the electron acceptor of the ET) that shows a strong and undesired background fluorescence at acidic pH. Our experimental results confirmed the theoretical predictions and d-PeT was observed for two of the sensors (with p-dimethylaminophenylethynyl substitution at 6- position of the carbazole core). For the third sensor (with phenylethynyl substitution at 6- position of the carbazole core), however, not d-PeT but rather the normal a-PeT was observed. The discrepancy between the DFT/TDDFT calculations and the experimental observations can be rationalized using free energy changes (Rehm-Weller equations) and the rate constants for the ET (k(ET), Marcus equation). These new d-PeT boronic acid sensors show improved photophysical properties compared to the known d-PeT sensor reported previously by us. In particular, the fluorescence transduction efficiency of the new sensors was improved 8-fold when compared to the known d-PeT boronic acid sensors. Novel fluorescence enhancement/reduction was observed for one of the sensors upon binding with mandelic acid or tartaric acid at pH 5.6. The effect of pH as well as the bonding with analytes on the emission of the sensors were rationalized using DFT/TDDFT calculations. We believe that rational sensor design aided by DFT/TDDFT calculations as well as using free energy changes and electron transfer rate constants to study the emission properties of PeT sensors will become an essential tool in the design of new fluorophores or fluorescent sensors with predetermined photophysical properties.

  DOI：

  10.1021/ja9060646
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 9-butyl-6-[4-(N,N-dimethylamino)]phenylethynyl-3-N-(4-fluoro)benzylaminomethylcarbazole
  参考文献：
  名称：

  Rational Design of d-PeT Phenylethynylated-Carbazole Monoboronic Acid Fluorescent Sensors for the Selective Detection of α-Hydroxyl Carboxylic Acids and Monosaccharides

  摘要：

  We have synthesized three new phenylethynylated carbazole boronic acid sensors, which were predicted to display novel d-PeT fluorescence transduction (PeT, photoinduced electron transfer; fluorophore as the electron donor of the electron transfer, ET) by DFT/TDDFT calculations. The d-PeT effect is characterized by a lower background fluorescence at acidic pH than at neutral pH, which is in stark contrast to the normal a-PeT effect (fluorophore as the electron acceptor of the ET) that shows a strong and undesired background fluorescence at acidic pH. Our experimental results confirmed the theoretical predictions and d-PeT was observed for two of the sensors (with p-dimethylaminophenylethynyl substitution at 6- position of the carbazole core). For the third sensor (with phenylethynyl substitution at 6- position of the carbazole core), however, not d-PeT but rather the normal a-PeT was observed. The discrepancy between the DFT/TDDFT calculations and the experimental observations can be rationalized using free energy changes (Rehm-Weller equations) and the rate constants for the ET (k(ET), Marcus equation). These new d-PeT boronic acid sensors show improved photophysical properties compared to the known d-PeT sensor reported previously by us. In particular, the fluorescence transduction efficiency of the new sensors was improved 8-fold when compared to the known d-PeT boronic acid sensors. Novel fluorescence enhancement/reduction was observed for one of the sensors upon binding with mandelic acid or tartaric acid at pH 5.6. The effect of pH as well as the bonding with analytes on the emission of the sensors were rationalized using DFT/TDDFT calculations. We believe that rational sensor design aided by DFT/TDDFT calculations as well as using free energy changes and electron transfer rate constants to study the emission properties of PeT sensors will become an essential tool in the design of new fluorophores or fluorescent sensors with predetermined photophysical properties.

  DOI：

  10.1021/ja9060646