(E)-3-(4-(1,5,9-trithia-13-azacyclohexadecan-13-yl)phenyl)-1-(4-cyanophenyl)prop-2-en-1-one | 1204823-68-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (E)-3-(4-(1,5,9-trithia-13-azacyclohexadecan-13-yl)phenyl)-1-(4-cyanophenyl)prop-2-en-1-one
• CAS: 1204823-68-6
• 化学式: C₂₈H₃₄N₂OS₃
• 分子量: 510.789
• InChiKey: FQOCMYFKHDYJFH-NTEUORMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.03
• 重原子数：
  34.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  44.1
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (E)-3-(4-(1,5,9-trithia-13-azacyclohexadecan-13-yl)phenyl)-1-(4-cyanophenyl)prop-2-en-1-one 、 五氨基氟丙基氢氧吡啶 在 溶剂黄146 作用下， 以15%的产率得到(+/-)-13-(4-(3-(4-cyanophenyl)-1-(perfluorophenyl)-4,5-dihydro-1H-pyrazol-5-yl)phenyl)-1,5,9-trithia-13-azacyclohexadecane
  参考文献：
  名称：

  Kinetically Controlled Photoinduced Electron Transfer Switching in Cu(I)-Responsive Fluorescent Probes

  摘要：

  Copper(I) -responsive fluorescent probes based on photoinduced electron transfer (PET) switching consistently display incomplete recovery of emission upon Cu(I) binding compared to the corresponding isolated fluorophores, raising the question of whether Cu(I) might engage in adverse quenching pathways. To address this question, we performed detailed photophysical studies on a series of Cu(I)-responsive fluorescent probes that are based on a 16-membered thiazacrown receptor ([16]aneNS(3)) tethered to 1,3,5-triarylpyrazoline-fluorophores. The fluorescence enhancement upon Cu(I) binding, which is mainly governed by changes in the photoinduced electron transfer (PET) driving force between the ligand and fluorophore, was systematically optimized by increasing the electron withdrawing character of the 1-aryl-ring, yielding a maximum 29-fold fluorescence enhancement upon saturation with Cu(I) in methanol and a greater than 500-fold enhancement upon protonation with trifluoroacetic acid. Time-resolved fluorescence decay data for the Cu(I)-saturated probe indicated the presence of three distinct emissive species in methanol. Contrary to the notion that Cu(I) might engage in reductive electron transfer quenching, femtosecond time-resolved pump-probe experiments provided no evidence for formation of a transient Cu(II) species upon photoexcitation. Variable temperature H-1 NMR experiments revealed a dynamic equilibrium between the tetradentate NS3-coordinated Cu(I) complex and a ternary complex involving coordination of a solvent molecule, an observation that was further supported by quantum chemical calculations. The combined photophysical, electrochemical, and solution chemistry experiments demonstrate that electron transfer from Cu(I) does not compete with radiative deactivation of the excited fluorophore, and, hence, that the Cu(I)-induced fluorescence switching is kinetically controlled.

  DOI：

  10.1021/ja908326z
• 作为产物：
  描述：

  对氰基苯乙酮 、 4-(1,5,9-trithia-13-azacyclohexadecan-13-yl)benzaldehyde 在 哌啶 作用下， 以 乙醇 为溶剂， 以80%的产率得到(E)-3-(4-(1,5,9-trithia-13-azacyclohexadecan-13-yl)phenyl)-1-(4-cyanophenyl)prop-2-en-1-one
  参考文献：
  名称：

  Kinetically Controlled Photoinduced Electron Transfer Switching in Cu(I)-Responsive Fluorescent Probes

  摘要：

  Copper(I) -responsive fluorescent probes based on photoinduced electron transfer (PET) switching consistently display incomplete recovery of emission upon Cu(I) binding compared to the corresponding isolated fluorophores, raising the question of whether Cu(I) might engage in adverse quenching pathways. To address this question, we performed detailed photophysical studies on a series of Cu(I)-responsive fluorescent probes that are based on a 16-membered thiazacrown receptor ([16]aneNS(3)) tethered to 1,3,5-triarylpyrazoline-fluorophores. The fluorescence enhancement upon Cu(I) binding, which is mainly governed by changes in the photoinduced electron transfer (PET) driving force between the ligand and fluorophore, was systematically optimized by increasing the electron withdrawing character of the 1-aryl-ring, yielding a maximum 29-fold fluorescence enhancement upon saturation with Cu(I) in methanol and a greater than 500-fold enhancement upon protonation with trifluoroacetic acid. Time-resolved fluorescence decay data for the Cu(I)-saturated probe indicated the presence of three distinct emissive species in methanol. Contrary to the notion that Cu(I) might engage in reductive electron transfer quenching, femtosecond time-resolved pump-probe experiments provided no evidence for formation of a transient Cu(II) species upon photoexcitation. Variable temperature H-1 NMR experiments revealed a dynamic equilibrium between the tetradentate NS3-coordinated Cu(I) complex and a ternary complex involving coordination of a solvent molecule, an observation that was further supported by quantum chemical calculations. The combined photophysical, electrochemical, and solution chemistry experiments demonstrate that electron transfer from Cu(I) does not compete with radiative deactivation of the excited fluorophore, and, hence, that the Cu(I)-induced fluorescence switching is kinetically controlled.

  DOI：

  10.1021/ja908326z