4-[2-[8-[2-(4-Aminophenyl)ethynyl]pyren-1-yl]ethynyl]aniline | 1161789-24-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 4-[2-[8-[2-(4-Aminophenyl)ethynyl]pyren-1-yl]ethynyl]aniline
• CAS: 1161789-24-7
• 化学式: C₃₂H₂₀N₂
• 分子量: 432.524
• InChiKey: OAGIADADNSNKQI-UHFFFAOYSA-N

物化性质

• 沸点：
  731.0±50.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  34
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-[2-[8-[2-(4-Aminophenyl)ethynyl]pyren-1-yl]ethynyl]aniline 、 2,4-二硝基苯磺酰氯 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 45.0h， 以20%的产率得到N-[4-[2-[8-[2-[4-[(2,4-dinitrophenyl)sulfonylamino]phenyl]ethynyl]pyren-1-yl]ethynyl]phenyl]-2,4-dinitrobenzenesulfonamide
  参考文献：
  名称：

  Tuning the Intramolecular Charge Transfer of Alkynylpyrenes: Effect on Photophysical Properties and Its Application in Design of OFF−ON Fluorescent Thiol Probes

  摘要：

  Green and yellow-emitting 1,6- and 1,8-bis(phenylethynyl) pyrenes (dyes 7, 8, 9, and 10) with different intramolecular charge transfer (ICT) feature were synthesized and the effect of ICT oil the photophysical properties of these derivatives were studied by UV-vis absorption spectra, fluorescence emission spectra, and DFT/TDDFT calculations. For the dyes with electron-pushing group (e.g., -dimethylamino, dye 8 and dye 10), structureless and solvent polarity-sensitive fluorescence emission spectra were observed. Conversely, dye with electron-withdrawing group (e.g., -CN, dye 7) shows structured and solvent polarity-independent emission spectra. OFF-ON fluorescent thiol probes 11 and 12 with 2,4-dinitrobenzenesulfonyl protected ethynylpyrene fluorophore were designed based oil DFT/TDDFT calculations, which predicts dark state (S-1) for these thiol probes (e.g.. oscillator strength f = 0.0086 for S-1 <- S-0 transition of die probe 11). This dark state is induced by the ICT effect with ethynylated pyrene fluorophore as electron donor and 2,4-dinitrobenzenesulfonyl unit as electron acceptor. Cleavage of the 2,4-dinitrobenzenesulfonyl unit by thiol releases the free fluorophore, for which the lowest-lying excited state S, is no longer a dark state, but an emissive state (f = 0.9776 for S-1 <- S-0 transition). These theoretical predictions on die photophysical properties of the molecular probes were fully proved by experimental results. Our results demonstrated that the fluorescence OFF-ON switching of this kind of thiol probe is due to the termination of the ICT effect (which quenches the emission, by a dark S, state) by cleavage of the 2,4-dinitrobenzenesulfonyl unit (as acceptor of ICT effect) with thiols, not the re-establishment of the D-pi-A feature of the fluorophore. These investigation on the pyrene derived green-emitting fluorophores and the DFT/TDDFT calculation aided probe design Suggest that future application of these results may prove useful toward the rational design of fluorophores or fluorescent probes with predetermined photophysical properties.

  DOI：

  10.1021/jo900588e
• 作为产物：
  描述：

  N-[4-[2-[8-[2-(4-aminophenyl)ethynyl]pyren-1-yl]ethynyl]phenyl]-2,4-dinitrobenzenesulfonamide 在 甲醇 、 L-半胱氨酸 、 水 作用下， 生成 4-[2-[8-[2-(4-Aminophenyl)ethynyl]pyren-1-yl]ethynyl]aniline
  参考文献：
  名称：

  Tuning the Intramolecular Charge Transfer of Alkynylpyrenes: Effect on Photophysical Properties and Its Application in Design of OFF−ON Fluorescent Thiol Probes

  摘要：

  Green and yellow-emitting 1,6- and 1,8-bis(phenylethynyl) pyrenes (dyes 7, 8, 9, and 10) with different intramolecular charge transfer (ICT) feature were synthesized and the effect of ICT oil the photophysical properties of these derivatives were studied by UV-vis absorption spectra, fluorescence emission spectra, and DFT/TDDFT calculations. For the dyes with electron-pushing group (e.g., -dimethylamino, dye 8 and dye 10), structureless and solvent polarity-sensitive fluorescence emission spectra were observed. Conversely, dye with electron-withdrawing group (e.g., -CN, dye 7) shows structured and solvent polarity-independent emission spectra. OFF-ON fluorescent thiol probes 11 and 12 with 2,4-dinitrobenzenesulfonyl protected ethynylpyrene fluorophore were designed based oil DFT/TDDFT calculations, which predicts dark state (S-1) for these thiol probes (e.g.. oscillator strength f = 0.0086 for S-1 <- S-0 transition of die probe 11). This dark state is induced by the ICT effect with ethynylated pyrene fluorophore as electron donor and 2,4-dinitrobenzenesulfonyl unit as electron acceptor. Cleavage of the 2,4-dinitrobenzenesulfonyl unit by thiol releases the free fluorophore, for which the lowest-lying excited state S, is no longer a dark state, but an emissive state (f = 0.9776 for S-1 <- S-0 transition). These theoretical predictions on die photophysical properties of the molecular probes were fully proved by experimental results. Our results demonstrated that the fluorescence OFF-ON switching of this kind of thiol probe is due to the termination of the ICT effect (which quenches the emission, by a dark S, state) by cleavage of the 2,4-dinitrobenzenesulfonyl unit (as acceptor of ICT effect) with thiols, not the re-establishment of the D-pi-A feature of the fluorophore. These investigation on the pyrene derived green-emitting fluorophores and the DFT/TDDFT calculation aided probe design Suggest that future application of these results may prove useful toward the rational design of fluorophores or fluorescent probes with predetermined photophysical properties.

  DOI：

  10.1021/jo900588e

文献信息

• Tuning the Intramolecular Charge Transfer of Alkynylpyrenes: Effect on Photophysical Properties and Its Application in Design of OFF−ON Fluorescent Thiol Probes
  作者：Shaomin Ji、Jun Yang、Qing Yang、Shasha Liu、Maodu Chen、Jianzhang Zhao

  DOI：10.1021/jo900588e

  日期：2009.7.3

  Green and yellow-emitting 1,6- and 1,8-bis(phenylethynyl) pyrenes (dyes 7, 8, 9, and 10) with different intramolecular charge transfer (ICT) feature were synthesized and the effect of ICT oil the photophysical properties of these derivatives were studied by UV-vis absorption spectra, fluorescence emission spectra, and DFT/TDDFT calculations. For the dyes with electron-pushing group (e.g., -dimethylamino, dye 8 and dye 10), structureless and solvent polarity-sensitive fluorescence emission spectra were observed. Conversely, dye with electron-withdrawing group (e.g., -CN, dye 7) shows structured and solvent polarity-independent emission spectra. OFF-ON fluorescent thiol probes 11 and 12 with 2,4-dinitrobenzenesulfonyl protected ethynylpyrene fluorophore were designed based oil DFT/TDDFT calculations, which predicts dark state (S-1) for these thiol probes (e.g.. oscillator strength f = 0.0086 for S-1 <- S-0 transition of die probe 11). This dark state is induced by the ICT effect with ethynylated pyrene fluorophore as electron donor and 2,4-dinitrobenzenesulfonyl unit as electron acceptor. Cleavage of the 2,4-dinitrobenzenesulfonyl unit by thiol releases the free fluorophore, for which the lowest-lying excited state S, is no longer a dark state, but an emissive state (f = 0.9776 for S-1 <- S-0 transition). These theoretical predictions on die photophysical properties of the molecular probes were fully proved by experimental results. Our results demonstrated that the fluorescence OFF-ON switching of this kind of thiol probe is due to the termination of the ICT effect (which quenches the emission, by a dark S, state) by cleavage of the 2,4-dinitrobenzenesulfonyl unit (as acceptor of ICT effect) with thiols, not the re-establishment of the D-pi-A feature of the fluorophore. These investigation on the pyrene derived green-emitting fluorophores and the DFT/TDDFT calculation aided probe design Suggest that future application of these results may prove useful toward the rational design of fluorophores or fluorescent probes with predetermined photophysical properties.