[5,15-bis[(4'-dimethylaminophenyl)ethynyl]-10,20-diphenylporphinato]Zn(II) | 184099-41-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [5,15-bis[(4'-dimethylaminophenyl)ethynyl]-10,20-diphenylporphinato]Zn(II)
• CAS: 184099-41-0
• 化学式: C₅₂H₃₈N₆Zn
• 分子量: 812.304
• InChiKey: KWYKRYUAGZYEBX-CXWHQIBLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [5,15-bis[(4'-dimethylaminophenyl)ethynyl]-10,20-diphenylporphinato]Zn(II) 在 盐酸 作用下， 以 氯仿 、 水 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Photophysical Investigation of Neutral and Diprotonated Free-Base Bis(Arylethynyl)porphyrins

  摘要：

  The photophysical properties for a series of free-base arylethynyl porphyrins and the corresponding trans-disubstituted tetraphenylporphyrin (H2TPP) derivatives lacking arylethynyl functionalities have been studied via electronic absorption and emission spectroscopy in both neutral and diacid forms. Enhanced substituent effects on porphyrin absorption spectra are observed in the arylethynyl porphyrins relative to the H2TPP derivatives, owing to the presence of the ethynyl spacer that allows for a coplanar geometry between the porphyrin macrocycle and the appended phenyl substituents. Upon protonation, both series of porphyrins exhibit substantially red shifted absorption and emission spectra and enhanced oscillator strengths, with the magnitude of the spectral shifts being more substantial in the presence of the ethynyl functionalities. Spectral features of the arylethynyl porphyrin bearing p-dimethylamino substituents closely resemble those previously classified as "hyperporphyrin spectra" and are indicative of excited-state charge-transfer character. Protonation of both series of porphyrins results in reduced fluorescence lifetimes and enhanced nonradiative decay rates, and the impact of protonation on these parameters is attenuated in the presence of the arylethynyl functionalities. Our results coupled with previous structural data showing that arylethynyl porphyrins exhibit less structural distortion upon diacid formation relative to H2TPP further substantiate the proposal that significant alteration of porphyrin photophysical properties upon diacid formation can be attributed to nonplanar structural distortions induced by protonation.

  DOI：

  10.1021/jp205309f
• 作为产物：
  描述：

  5-苯基联吡咯甲烷 在 copper(l) iodide 、 四(三苯基膦)钯 、 zinc diacetate 、 三氟化硼乙醚 、 四丁基氟化铵 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 [5,15-bis[(4'-dimethylaminophenyl)ethynyl]-10,20-diphenylporphinato]Zn(II)
  参考文献：
  名称：

  Photophysical Investigation of Neutral and Diprotonated Free-Base Bis(Arylethynyl)porphyrins

  摘要：

  The photophysical properties for a series of free-base arylethynyl porphyrins and the corresponding trans-disubstituted tetraphenylporphyrin (H2TPP) derivatives lacking arylethynyl functionalities have been studied via electronic absorption and emission spectroscopy in both neutral and diacid forms. Enhanced substituent effects on porphyrin absorption spectra are observed in the arylethynyl porphyrins relative to the H2TPP derivatives, owing to the presence of the ethynyl spacer that allows for a coplanar geometry between the porphyrin macrocycle and the appended phenyl substituents. Upon protonation, both series of porphyrins exhibit substantially red shifted absorption and emission spectra and enhanced oscillator strengths, with the magnitude of the spectral shifts being more substantial in the presence of the ethynyl functionalities. Spectral features of the arylethynyl porphyrin bearing p-dimethylamino substituents closely resemble those previously classified as "hyperporphyrin spectra" and are indicative of excited-state charge-transfer character. Protonation of both series of porphyrins results in reduced fluorescence lifetimes and enhanced nonradiative decay rates, and the impact of protonation on these parameters is attenuated in the presence of the arylethynyl functionalities. Our results coupled with previous structural data showing that arylethynyl porphyrins exhibit less structural distortion upon diacid formation relative to H2TPP further substantiate the proposal that significant alteration of porphyrin photophysical properties upon diacid formation can be attributed to nonplanar structural distortions induced by protonation.

  DOI：

  10.1021/jp205309f

文献信息

• Exceptional Electronic Modulation of Porphyrins through <i>meso</i>-Arylethynyl Groups. Electronic Spectroscopy, Electronic Structure, and Electrochemistry of [5,15-Bis[(aryl)ethynyl]- 10,20-diphenylporphinato]zinc(II) Complexes. X-ray Crystal Structures of [5,15-Bis[(4‘-fluorophenyl)ethynyl]- 10,20-diphenylporphinato]zinc(II) and 5,15-Bis[(4‘-methoxyphenyl)ethynyl]-10,20-diphenylporphyrin
  作者：Steven M. LeCours、Stephen G. DiMagno、Michael J. Therien

  DOI：10.1021/ja962403y

  日期：1996.1.1

  thynyl]-10,20-diphenylporphinato]zinc(II), [5,15-bis[(4‘-methoxyphenyl)ethynyl]-10,20-diphenylporphinato]zinc(II), [5,15-bis[(phenyl)ethynyl]-10,20-diphenylporphinato]zinc(II), [5,15-bis[(4‘-fluorophenyl)ethynyl]-10,20-diphenylporphinato]zinc(II), and [5,15-bis[(4‘-nitrophenyl)ethynyl]-10,20-diphenylporphinato]zinc(II). The X-ray structure of one of these complexes, [5,15-bis[(4‘-fluorophenyl)ethynyl]-10

  描述了一类新的卟啉，其中插入的乙炔基部分将芳基连接到卟啉的 5-和 15-位。报道了五种新化合物的合成和光谱学：[5,15-双[(4'-二甲基氨基苯基)乙炔基]-10,20-二苯基卟吩基]锌(II)、[5,15-双[(4'-甲氧基苯基)乙炔基]-10,20-二苯基卟吩基]锌(II), [5,15-双[(苯基)乙炔基]-10,20-二苯基卟吩基]锌(II), [5,15-二[(4') -氟苯基)乙炔基]-10,20-二苯基卟吩基]锌(II)和[5,15-双[(4'-硝基苯基)乙炔基]-10,20-二苯基卟吩基]锌(II)。其中一种配合物 [5,15-双[(4'-氟苯基)乙炔基]-10,20-二苯基卟吩基]锌 (II) 的 X 射线结构很不寻常，因为它显示了芳基乙炔基-苯环与卟啉大环共面。