zinc(II) 5,15-di(3,5-di-tert-butylphenyl)-10-phenylporphyrin | 865535-93-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: zinc(II) 5,15-di(3,5-di-tert-butylphenyl)-10-phenylporphyrin
• CAS: 865535-93-9
• 化学式: C₅₄H₅₆N₄Zn
• 分子量: 826.455
• InChiKey: KVLXSIPFCVDNFN-PORWGZQWSA-N

计算性质

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

• 作为反应物：
  描述：

  zinc(II) 5,15-di(3,5-di-tert-butylphenyl)-10-phenylporphyrin 在 [双(三氟乙酰氧基)碘]苯 、 sodium tetrahydroborate 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 反应 0.58h， 以86%的产率得到C₁₀₈H₁₁₀N₈Zn₂
  参考文献：
  名称：

  An Efficient PIFA-Mediated Synthesis of Fused Diporphyrin and Triply−Singly Interlacedly Linked Porphyrin Array

  摘要：

  An efficient and metal-free oxidative method was reported for synthesis of triply linked diporphyrins with 2.5 equiv of phenyliodine bis(trifluoroacetate) (PIFA). This reaction showed high selectivity for Zn(II) porphyrins and had been successfully applied in the synthesis of a novel triply-singly interlacedly linked porphyrin array with lower energy gap.

  DOI：

  10.1021/ol902198w
• 作为产物：
  描述：

  5,15-di(3,5-di-tert-butylphenyl)-10-phenylporphyrin 在 zinc diacetate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到zinc(II) 5,15-di(3,5-di-tert-butylphenyl)-10-phenylporphyrin
  参考文献：
  名称：

  Synthesis of new azido porphyrins and their reactivity in copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction with alkynes

  摘要：

  We report herein the preparation of two novel porphyrins substituted with an azido group born either on the para-position of one phenyl meso-susbtituent of a tetraaryl zinc porphyrin (1) or directly on the meso-position of a trisaryl nickel porphyrin (2). We studied the scope and the limitation the Huisgen cycloaddition reaction of these two porphyrins using different catalytic conditions. We observed that the carbene (SlMes)CuBr in THF/H2O 3:1 at 45 degrees C for 60 h gives almost quantitative yields for the reaction between I and different alkynes, but significantly lower yields with 2 probably due to its thermal instability. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.07.049

文献信息

• 2,3-Dicyano-5,6-dichlorobenzoquinone-Mediated and Selective C–O and C–C Cross-Couplings of Phenols and Porphyrins
  作者：Qi Cheng、Zheng Wang、Hong-Wei Li、Chang-Yu Shan、Peng-Fei Zheng、Li Shuai、Yu-Long Li、Ying-Chun Chen、Qin Ouyang

  DOI：10.1021/acs.orglett.9b04330

  日期：2020.1.3

  cross-coupling reaction between porphyrins and phenols has been developed through 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ)/Sc(OTf)3 oxidation, efficiently delivering meso-etherified porphyrins in good yields (≤93%). The radical complex process was proposed and calculated as the rationalized mechanism to block the homocoupling process. In addition, the switchable selective C-C cross-coupling reaction was achieved

  通过2,3-二氰基-5,6-二氯苯醌（DDQ）/ Sc（OTf）3的氧化反应，开发了卟啉与酚类之间的选择性CO交叉偶联反应，可有效地以良好的收率（≤93％）输送内醚化的卟啉）。提出了自由基复杂过程并将其计算为阻止均偶联过程的合理机制。此外，通过在DDQ氧化条件下使用大体积的富电子酚和萘酚可实现选择性的CC交叉偶联反应。
• Truxene-bridged Bodipy fullerene tetrads without precious metals: study of the energy transfer and application in triplet–triplet annihilation upconversion
  作者：Yuanyuan Che、Xuemei Yuan、Lei Sun、Haijun Xu、Xiaoyu Zhao、Fangjian Cai、Lang Liu、Jianzhang Zhao

  DOI：10.1039/d0tc03490h

  日期：——

  absorption coefficient is up to 5.63 × 105 M−1 cm−1 at 428 nm for T-B-C60-P. These tetrads show efficient singlet energy transfer from the Bodipy moiety to the fullerene/Zn–porphyrin moiety, the energy transfer rate constant is 2.72 × 109 s−1 and the efficiency is up to 90% for T-2B-C60. Electrochemical and computational studies show that T-B-C60-P exhibits photo electron transfer from fullerene to Zn–porphyrin

  富勒烯可以有效地产生三重态，而不会引起重原子效应。然而，它们在可见光谱范围内的弱吸收使得富勒烯不是理想的三重态光敏剂（PS）。在此，通过连接Bodipy或Zn-卟啉单元（T-2B-C 60和TBC 60 -P）制备新的戊二烯桥联富勒烯和Bodipy四联体，它们在可见光谱范围内显示出更强的吸收带，并且具有最大的摩尔吸收对于TBC 60 -P，在428 nm时系数最大为5.63×10 5 M -1 cm -1。这些四分体显示出从Bodipy部分到富勒烯/ Zn-卟啉部分的有效单线态能量转移，能量转移速率常数为2.72×10 9 s -1，对于T-2B-C 60效率高达90％。电化学和计算研究表明，TBC 60 -P表现出从富勒烯到Zn-卟啉的光电子转移，并形成了TBC 60 - ˙-P + ˙电荷分离态。纳秒时间分辨的瞬态差异吸收光谱表明，TBC 60 -P的三重态激发态富勒烯部分和Zn-卟啉
• One-pot reaction of aminoarenes and porphyrin – A fused amino acid-tetraphyrin(1.1.1.1) hybrid
  作者：Karolina Urbańska、Miłosz Pawilicki

  DOI：10.1142/s1088424621501248

  日期：2021.10

  Tetraphyrins(1.1.1.1) (Porphyrins) were merged with amino acids forming a direct bond between a meso-position of macrocycle and a nitrogen available in the side chain of the amino acid. The following intramolecular fusion observed for a free base porphyrin forms a structure with extended [Formula: see text]-delocalisation on the additional carbocyclic fragment, that substantially modifies the observed absorption and emission. A further modulation of electron behaviour has been observed for a deprotonated form of the fused system. A nitrogen atom introduced into the system can be treated as a switching factor that controls the delocalisation significantly influencing the emission by shifting between the available amine and imine tautomeric forms.

  四卟啉（1.1.1.1）（卟啉）与氨基酸合并，在大环的中位和氨基酸侧链中的氮之间形成直接键。自由基卟啉的分子内融合形成了一种结构，在额外的碳环片段上具有扩展的[式：见正文]异定位，从而大大改变了所观察到的吸收和发射。在融合体系的去质子化形式中，还观察到电子行为的进一步变化。引入该体系的氮原子可被视为一个开关因子，通过在现有的胺和亚胺同分异构形式之间转换，控制着对发射有重大影响的脱局域。
• Enhanced coherence by coupling spins through a delocalized π-system: Vanadyl porphyrin dimers
  作者：Iago Pozo、Zhijie Huang、Federico Lombardi、Dimitris I. Alexandropoulos、Fanmiao Kong、Michael Slota、Igor Tkach、Marina Bennati、Jie-Ren Deng、Wojciech Stawski、Peter N. Horton、Simon J. Coles、William K. Myers、Lapo Bogani、Harry L. Anderson

  DOI：10.1016/j.chempr.2023.09.013

  日期：2024.1

  prime candidates for molecular quantum units. One long-standing question is how to obtain a scaffold that connects multiple centers and allows two communication modalities: magnetic and electronic. We have synthesized and studied a selection of vanadyl porphyrin dimers as models of the most synthetically accessible linear porphyrin arrays. We show that a strongly π-conjugated backbone places the magnetic

  钒（IV）磁中心是分子量子单元的主要候选者。一个长期存在的问题是如何获得一种连接多个中心并允许两种通信方式的支架：磁性和电子。我们合成并研究了一系列氧钒卟啉二聚体，作为最容易合成的线性卟啉阵列的模型。我们表明，强 π 共轭骨架将磁系统置于以交换耦合 () 为主的中间状态，并保护量子相干性免受低温 (<10 K) 下电子对翻转过程的影响。这一结果是设计用于由微波和电读出控制的单分子器件的分子材料的一个基本步骤。
• State-Selective Electron Transfer in an Unsymmetric Acceptor−Zn(II)porphyrin−Acceptor Triad: Toward a Controlled Directionality of Electron Transfer from the Porphyrin S₂ and S₁ States as a Basis for a Molecular Switch
  作者：Staffan Wallin、Cyrille Monnereau、Errol Blart、Jean-Richard Gankou、Fabrice Odobel、Leif Hammarström

  DOI：10.1021/jp907824d

  日期：2010.2.4

  A series of Zn(II) porphyrin (ZnP) compounds covalently linked to different electron acceptor units, naphthaleneimide (NI) and naphthalenedimide (NDI), are reported. The aim was to demonstrate a state-selective direction of electron transfer, where excitation to the lowest excited S-1 state of the porphyrin (Q-band excitation) would give electron transfer to the NDI unit, while excitation to the higher S-2 state (Soret-hand excitation) would give electron transfer to the NI unit. This would constitute a basis for an opto-electronic Switch in which the direction of electron transfer and the resulting dipole moment can be controlled by using light input of different color. Indeed, electron transfer from the S-1 state to NDI Occurred in solvents of both high and low polarity, whereas no electron transfer to NDI was observed from the S-2 state. With NI as acceptor instead, very rapid (tau = 200-400 fs) electron transfer from the S-2 state occurred in all solvents. This was followed by an ultrafast (tau approximate to 100 fs) recombination to Populate the porphyrin S-1 state in nearly quantitative yield. The charge-separated state ZnP+NI- was spectroscopically observed, and evidence was obtained that recombination Occurred from a vibrationally excited ("hot") ZnP+NI- state in the more polar solvents. In these solvents, the thermally relaxed ZnP+NI- state lies at lower energy than the S-1 state so that further charge separation occurred from S-1 to form ZnP+NI-. This resulted in a highly unusual "ping-pong" sequence where the reaction went back and forth between locally excited ZnP states and charge-separated states: S-2 double right arrow ZnP+NI"hot"- double right arrow S-1 double right arrow ZnP+NI- double right arrow S-0. The electron transfer dynamics and its solvent dependence are discussed, as well as the function of the present Molecules as molecular switches.