[5,15-di(4-ethynylbenzyl)-10,20-diphenylporphinato]zinc(II) | 184099-43-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 英文名称: [5,15-di(4-ethynylbenzyl)-10,20-diphenylporphinato]zinc(II)
• 英文别名: [5,15-bis[(phenyl)ethynyl]-10,20-diphenylporphinato]Zn(II)
• CAS: 184099-43-2
• 化学式: C₄₈H₂₈N₄Zn
• 分子量: 726.167
• InChiKey: IZTHTAVMQRHBSC-RVGNQQIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.04
• 重原子数：
  53.0
• 可旋转键数：
  2.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [5,15-di(4-ethynylbenzyl)-10,20-diphenylporphinato]zinc(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：

  5,15-bis(trimethylsilanylethynyl)-10,20-diphenyl-21H,23H-porphyrin 在 copper(l) iodide 、 四(三苯基膦)钯 、 zinc diacetate 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 [5,15-di(4-ethynylbenzyl)-10,20-diphenylporphinato]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

• 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。
• Fundamental Study on Arsenic(III) Halides (AsX₃; X = Br, I) toward the Construction of <i>C</i>₃-Symmetrical Monodentate Arsenic Ligands
  作者：Susumu Tanaka、Masafumi Konishi、Hiroaki Imoto、Yuma Nakamura、Masatoshi Ishida、Hiroyuki Furuta、Kensuke Naka

  DOI：10.1021/acs.inorgchem.0c00598

  日期：2020.7.20

  Arsenic ligands have attracted considerable attention in coordination chemistry. Arsenic(III) halides are the most important starting materials in the preparation of monodentate arsenic ligands. In this work, we optimized the synthetic methodologies of arsenic(III) halides (AsX3; X = Br, I) and examined the difference of their physical properties such as solubility to organic solvent and reactivity

  砷配体在配位化学中引起了相当大的关注。卤化砷（III）是制备单齿砷配体的最重要原料。在这项工作中，我们优化了卤化砷（III）（AsX 3； X = Br，I）的合成方法，并研究了其物理性质的差异，例如对有机溶剂的溶解度和对亲核试剂的反应性。此外，用获得的AsX 3制备了多种单齿砷配体。最后，将所获得的单齿砷配体用于与卟啉的反应体系中的无铜Sonogashira交叉偶联反应。结果表明，单齿砷配体比三苯基膦具有更高的催化活性，这是由于砷和磷原子之间的孤对电子特性不同。
• Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks
  作者：Ho-Jin Son、Shengye Jin、Sameer Patwardhan、Sander J. Wezenberg、Nak Cheon Jeong、Monica So、Christopher E. Wilmer、Amy A. Sarjeant、George C. Schatz、Randall Q. Snurr、Omar K. Farha、Gary P. Wiederrecht、Joseph T. Hupp

  DOI：10.1021/ja310596a

  日期：2013.1.16

  Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal-organic frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts [5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinato]zinc(II) and [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II), respectively, were investigated. From fluorescence quenching experiments and theoretical calculations, we find that the photogenerated exciton migrates over a net distance of up to similar to 45 porphyrin struts within its lifetime in DA-MOF (but only similar to 3 in F-MOF), with a high anisotropy along a specific direction. The remarkably efficient exciton migration in DA-MOF is attributed to enhanced p-conjugation through the addition of two acetylene moieties in the porphyrin molecule, which leads to greater Q-band absorption intensity and much faster exciton-hopping (energy transfer between adjacent porphyrin struts). The long distance and directional energy migration in DA-MOF suggests promising applications of this compound or related compounds in solar energy conversion schemes as an efficient light-harvesting and energy-transport component.
• Synthesis of phenylethyne-linked porphyrin dyads
  作者：Kin-ya Tomizaki、Andrey B Lysenko、Masahiko Taniguchi、Jonathan S Lindsey

  DOI：10.1016/j.tet.2004.01.003

  日期：2004.2

  Four new porphyrin dyads have been prepared for studies in artificial photosynthesis. The two porphyrins are joined at the meso positions via a phenylethyne linker and are present in zinc/zinc or zinc/free base metalation states. The porphyrin bearing the ethynyl unit incorporates zero, one, or two pentafluorophenyl groups at non-linking meso positions for tuning the porphyrin redox potentials. The synthetic approach entailed Pd-mediated coupling of porphyrin building blocks that bear a single ethynylphenyl or bromo/iodo substituent. (C) 2004 Elsevier Ltd. All rights reserved.