[5,15-bis(ethynyl)-10,20-diphenylporphinato]zinc(II) | 156821-65-7

• 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(ethynyl)-10,20-diphenylporphinato]zinc(II)
• 英文别名: [5,15-diethynyl-10,20-diphenylporphinato]zinc(II)；5,15-diethynyl-10,20-diphenylporphyrin zinc(II)
• CAS: 156821-65-7
• 化学式: C₃₆H₂₀N₄Zn
• 分子量: 573.972
• InChiKey: ARHRQCJSHRUXNG-JGERCFRHSA-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(ethynyl)-10,20-diphenylporphinato]zinc(II) 在 盐酸 、 copper(l) iodide 、 四(三苯基膦)钯 、 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：

  5-苯基联吡咯甲烷 在 三氟化硼乙醚 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 [5,15-bis(ethynyl)-10,20-diphenylporphinato]zinc(II)
  参考文献：
  名称：

  Spectroscopic characterization of free-base hydroxy(arylethynyl)porphyrins in acidic and basic media

  摘要：

  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。

  DOI：

  10.1142/s1088424617500675

文献信息

• 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。
• 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。
• Synthesis of Porphyrin and Bacteriochlorin Glycoconjugates through CuAAC Reaction Tuning
  作者：Matthew C. Bennion、Morgan A. Burch、David G. Dennis、Melissa E. Lech、Kira Neuhaus、Nikole L. Fendler、Matthew R. Parris、Jessica E. Cuadra、Charlie F. Dixon、George T. Mukosera、David N. Blauch、Laura Hartmann、Nicole L. Snyder、Joshua V. Ruppel

  DOI：10.1002/ejoc.201901128

  日期：2019.10.17

  access to a series of unique porphyrin and bacteriochlorin glycoconjugates, including meso-glycosylated porphyrins and bacteriochlorins, and beta-glycosylated porphyrins, via copper catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) is reported for the first time. The work presented highlights the system-dependent reaction conditions required for glycosylation to porphyrins and bacteriochlorins based

  首次报道了通过铜催化叠氮炔 1,3-偶极环加成 (CuAAC) 快速、可重复地获得一系列独特的卟啉和菌绿素糖缀合物，包括内消旋糖基化卟啉和菌绿素以及 β-糖基化卟啉。该工作强调了基于每个环系统独特的电子特性，糖基化为卟啉和菌绿素所需的系统依赖性反应条件。使用弱化反应条件合成了 15 种新的糖基化卟啉和菌绿素类似物，产率为 74 - 99%，并将其扩展到固体支持物上，以生产第一个基于寡（酰氨基胺）的卟啉糖缀合物。这些化合物作为下一代水溶性催化剂和光动力疗法/光动力失活（PDT/PDI）剂具有巨大的潜力。
• Synthesis, Electronic Structure, and Electron Transfer Dynamics of (Aryl)ethynyl-Bridged Donor−Acceptor Systems
  作者：Naomi P. Redmore、Igor V. Rubtsov、Michael J. Therien

  DOI：10.1021/ja021278p

  日期：2003.7.1

  The ET dynamics of a series of donor-spacer-acceptor (D-Sp-A) systems featuring (porphinato)zinc(II), (aryl)ethynyl bridge, and arene diimide units were investigated by pump-probe transient absorption spectroscopy. Analysis of these data within the context of the Marcus-Levich-Jortner equation suggests that the pi-conjugated (aryl)ethynyl bridge plays an active role in the charge recombination (CR) reactions of these species by augmenting the extent of (porphinato)zinc(II) cation radical electronic delocalization; this increase in cation radical size decreases the reorganization energy associated with the CR reaction and thereby attenuates the extent to which the magnitudes of the CR rate constants are solvent dependent. The symmetries of porphyrin-localized HOMO and HOMO-1, the energy gap between these two orbitals, and D-A distance appear to play key roles in determining whether the (aryl)ethynyl bridge simply mediates electronic superexchange or functions as an integral component of the D and A units.