4-(pyridinyloxy)fluorescein ethyl ester

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 4-(pyridinyloxy)fluorescein ethyl ester
• 英文别名: Ethyl 2-[3-oxo-6-(pyridin-4-ylmethoxy)xanthen-9-yl]benzoate；ethyl 2-[3-oxo-6-(pyridin-4-ylmethoxy)xanthen-9-yl]benzoate
• 化学式: C₂₈H₂₁NO₅
• 分子量: 451.478
• InChiKey: SWWMVDBUGSIEJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  74.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [((Me)2bpb)Ru(NO)(Cl)] 、 4-(pyridinyloxy)fluorescein ethyl ester 、 silver perchlorate 以 乙腈 为溶剂， 反应 18.0h， 以27%的产率得到[(Me₂bpb)Ru(NO)(PyFlEt)]ClO₄
  参考文献：
  名称：

  Evidence of dexter energy transfer in NO photolability of dye-sensitized ruthenium nitrosyls

  摘要：

  Direct attachment of light-harvesting dye molecules to the ruthenium center of designed {Ru-NO}(6) nitrosyls has been shown to exhibit enhanced light-induced NO photorelease upon exposure to visible light. Theoretical studies have indicated that orbital overlap between the MOs of the dye and the nitrosyl units are key for such sensitization. In order to check whether altering the electronic conjugation between these two units causes reduction in the extent of sensitization, we have synthesized a pyridinyloxy-fluorescein dye PyFlEt and attached it to two designed ruthenium nitrosyls through the pyridine-N donor of the pyridinyloxy-end. The quantum yield values of NO photodissociation at 500 nm (phi(NO)) and fluorescence quantum yield values (phi(Fl)) of these two nitrosyl-dye conjugates namely, [(Me)(2)bpb)Ru(NO)(PyFlEt)]ClO4 (1-PyFlEt) and [((OMe)(2)IQ1)Ru(NO)(PyFlEt)]BF4 (2-PyFlEt) have been compared with those of [(Me)(2)bpb)Ru(NO)(FlEt)]ClO4 (1-FlEt) and [((OMe)(2)IQ1)Ru(NO)(FlEt)]BF4 (2-FlEt) in which the same FlEt dye is directly attached through the phenolato-O donor. This minor alteration in the linkage between the dye and the nitrosyl unit has caused significant reduction in the phi(NO) values of 1-PyFlEt and 2-PyFlEt while their phi(Fl) values have shown moderate improvement. These results strongly suggest that the light energy absorbed by the dye unit is transferred to the Ru-NO moiety through the Dexter pathway. If the electronic overlap is disrupted, only part of the energy is used in NO photorelease and a significant portion is lost through fluorescence. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.04.034
• 作为产物：
  描述：

  4-吡啶甲醇 、 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 40.0h， 以80%的产率得到4-(pyridinyloxy)fluorescein ethyl ester
  参考文献：
  名称：

  Evidence of dexter energy transfer in NO photolability of dye-sensitized ruthenium nitrosyls

  摘要：

  Direct attachment of light-harvesting dye molecules to the ruthenium center of designed {Ru-NO}(6) nitrosyls has been shown to exhibit enhanced light-induced NO photorelease upon exposure to visible light. Theoretical studies have indicated that orbital overlap between the MOs of the dye and the nitrosyl units are key for such sensitization. In order to check whether altering the electronic conjugation between these two units causes reduction in the extent of sensitization, we have synthesized a pyridinyloxy-fluorescein dye PyFlEt and attached it to two designed ruthenium nitrosyls through the pyridine-N donor of the pyridinyloxy-end. The quantum yield values of NO photodissociation at 500 nm (phi(NO)) and fluorescence quantum yield values (phi(Fl)) of these two nitrosyl-dye conjugates namely, [(Me)(2)bpb)Ru(NO)(PyFlEt)]ClO4 (1-PyFlEt) and [((OMe)(2)IQ1)Ru(NO)(PyFlEt)]BF4 (2-PyFlEt) have been compared with those of [(Me)(2)bpb)Ru(NO)(FlEt)]ClO4 (1-FlEt) and [((OMe)(2)IQ1)Ru(NO)(FlEt)]BF4 (2-FlEt) in which the same FlEt dye is directly attached through the phenolato-O donor. This minor alteration in the linkage between the dye and the nitrosyl unit has caused significant reduction in the phi(NO) values of 1-PyFlEt and 2-PyFlEt while their phi(Fl) values have shown moderate improvement. These results strongly suggest that the light energy absorbed by the dye unit is transferred to the Ru-NO moiety through the Dexter pathway. If the electronic overlap is disrupted, only part of the energy is used in NO photorelease and a significant portion is lost through fluorescence. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.04.034

文献信息

• Evidence of dexter energy transfer in NO photolability of dye-sensitized ruthenium nitrosyls
  作者：Tara R. deBoer-Maggard、Nicole L. Fry、Pradip K. Mascharak

  DOI：10.1016/j.ica.2013.04.034

  日期：2013.9

  Direct attachment of light-harvesting dye molecules to the ruthenium center of designed Ru-NO}(6) nitrosyls has been shown to exhibit enhanced light-induced NO photorelease upon exposure to visible light. Theoretical studies have indicated that orbital overlap between the MOs of the dye and the nitrosyl units are key for such sensitization. In order to check whether altering the electronic conjugation between these two units causes reduction in the extent of sensitization, we have synthesized a pyridinyloxy-fluorescein dye PyFlEt and attached it to two designed ruthenium nitrosyls through the pyridine-N donor of the pyridinyloxy-end. The quantum yield values of NO photodissociation at 500 nm (phi(NO)) and fluorescence quantum yield values (phi(Fl)) of these two nitrosyl-dye conjugates namely, [(Me)(2)bpb)Ru(NO)(PyFlEt)]ClO4 (1-PyFlEt) and [((OMe)(2)IQ1)Ru(NO)(PyFlEt)]BF4 (2-PyFlEt) have been compared with those of [(Me)(2)bpb)Ru(NO)(FlEt)]ClO4 (1-FlEt) and [((OMe)(2)IQ1)Ru(NO)(FlEt)]BF4 (2-FlEt) in which the same FlEt dye is directly attached through the phenolato-O donor. This minor alteration in the linkage between the dye and the nitrosyl unit has caused significant reduction in the phi(NO) values of 1-PyFlEt and 2-PyFlEt while their phi(Fl) values have shown moderate improvement. These results strongly suggest that the light energy absorbed by the dye unit is transferred to the Ru-NO moiety through the Dexter pathway. If the electronic overlap is disrupted, only part of the energy is used in NO photorelease and a significant portion is lost through fluorescence. (C) 2013 Elsevier B. V. All rights reserved.