5,15-bis(trimethylsilylethynyl)-10,20-diphenylporphyrin zinc(II) | 156821-56-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,15-bis(trimethylsilylethynyl)-10,20-diphenylporphyrin zinc(II)
• CAS: 156821-56-6
• 化学式: C₄₂H₃₆N₄Si₂Zn
• 分子量: 718.336
• InChiKey: XYCFIFDFWXSIDH-BNNLMONQSA-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(trimethylsilylethynyl)-10,20-diphenylporphyrin zinc(II) 在 盐酸 、 copper(l) iodide 、 四(三苯基膦)钯 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 、 水 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：

  3-三甲基甲硅烷基丙炔醛 在 zinc diacetate 、 三氟化硼乙醚 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 生成 5,15-bis(trimethylsilylethynyl)-10,20-diphenylporphyrin zinc(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

• Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT calculations
  作者：Baris Temelli、Mine Gündüz、Dilek Yüksel

  DOI：10.1016/j.tet.2018.07.007

  日期：2018.8

  porphyrin-corrole dyads and triads were synthesized by using Pd(0) mediated coupling reactions and their structures were characterized by NMR, FT-IR, UV/Vis and fluorescence techniques. Besides spectroscopic techniques, computational studies at B3LYP/6-311G(d,p) level of DFT were also used to elucidate the minimum energy geometries and the molecular orbital characteristics of the new dyads and triads. DFT

  使用Pd（0）介导的偶联反应合成乙炔桥卟啉-corrole二联体和三联体，并通过NMR，FT-IR，UV / Vis和荧光技术对其结构进行表征。除光谱技术外，在DFT的B3LYP / 6-311G（d，p）水平进行的计算研究还用于阐明最小能量几何结构以及新二元组和三元组的分子轨道特征。DFT计算指出，在二元组和三元组的大环之间存在电荷分离的供体-受体性质，发射研究表明大环之间存在激发态相互作用，并且能量从卟啉传递至Corrole单元。
• Spectroscopic characterization of free-base hydroxy(arylethynyl)porphyrins in acidic and basic media
  作者：Kaarin K. Evens、Kathryn E. Splan

  DOI：10.1142/s1088424617500675

  日期：2017.10

  The addition of arylethynyl groups to the porphyrin macrocycle represents an effective strategy with which to enhance the light-harvesting properties of porphyrins. We now extend this modification to arylethynyl porphyrins with two or four [Formula: see text]-hydroxyphenyl substituents. Arylethynyl porphyrins bearing four, but not two, [Formula: see text]-hydroxyphenyl substituents show evidence of aggregation under acidic conditions. Under basic conditions, deprotonation of the peripheral hydroxyphenyl substituents results in substantially red-shifted spectral features and enhanced absorption in the Q-band region. When the hydroxyphenyl groups are appended to the porphyrin macrocylce via the ethynyl spacers, the spectral shifts observed upon deprotonation are significantly enhanced relative to those observed for hydroxyphenylporphyrins, highlighting the role of expanded conjugation in altering porphyrin photophysics.

  在卟啉大环上添加芳基乙炔基团是增强卟啉光收集特性的有效策略。现在，我们将这种改性扩展到具有两个或四个[式中：见正文]羟基取代基的芳炔基卟啉。在酸性条件下，具有四个而非两个[式：见正文]-羟基苯基取代基的芳炔基卟啉会出现聚集现象。在碱性条件下，外围羟基苯基取代基的去质子化会导致光谱特征大幅红移，并增强 Q 波段区域的吸收。当羟苯基基团通过乙炔基间隔附加到卟啉大二茂体上时，与羟苯基卟啉相比，在去质子化时观察到的光谱偏移显著增强，这突出表明了扩展共轭在改变卟啉光物理中的作用。