(NO2Ph)Ph3PorPd | 1065473-90-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (NO2Ph)Ph3PorPd
• 英文别名: 5-(4-nitrophenyl)-10,15,20-triphenylporphyrinatopalladium(II)；(NO₂Ph)Ph₃PorPd；NO2-PdTPP；Pd(5-(4-nitrophenyl)-10,15,20-triphenylporphyrin)
• CAS: 1065473-90-6
• 化学式: C₄₄H₂₇N₅O₂Pd
• 分子量: 764.151
• InChiKey: ZLJWNFOFFGHTMZ-DAJBKUBHSA-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：
  None
• 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：

  (NO2Ph)Ph3PorPd 在 盐酸 、 tin(II) chloride dihydrate 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 48.0h， 以50%的产率得到Pd(II)-5-(4-aminophenyl)-10,15,20-tetraphenylporphyrin
  参考文献：
  名称：

  金属卟啉-tri三羰基联吡啶组装体中的远程位点光饱和：具有非常短寿命的激发态的分子的光反应。

  摘要：

  合成了一系列金属卟啉（和相应的游离碱卟啉）的合成，这些金属卟啉通过一个苯基的4位上的酰胺键被联吡啶基单-间位取代：[Re（CO）（3） （Pic）Bpy-MTPP] [OTf]，其中M = Mg，Zn，Pd或2H，Pic = 3-甲基吡啶，Bpy = 2,2'-联吡啶，TPP =四苯基卟啉。组件与牺牲电子供体三乙胺的光化学反应已通过红外光谱进行了研究，并与不含without的Bpy-MTPP类型类似物的行为进行了比较。在过量的甲基吡啶存在下对金属卟啉单元的选择性长波照射导致leads联吡啶中心的还原。在不存在3-甲基吡啶的情况下，后者不被还原，而是被添加的卤化物或THF溶剂取代。机理分析突出显示了一方面锌和镁螯合物与另一方面卟啉钯之间的差异。游离基程序集[Re（CO）（3）（Pic）Bpy-H（2）TPP] [OTf]不起作用。锌和镁卟啉组装体在经历光诱导的内部球电子从三乙胺转移以形成组装

  DOI：

  10.1039/b806267f
• 作为产物：
  描述：

  tetraphenylporphyrin 在 三氟乙酸 、 sodium nitrite 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.05h， 生成 (NO2Ph)Ph3PorPd
  参考文献：
  名称：

  Ruthenium and Osmium Complexes of Phosphine-Porphyrin Derivatives as Potential Bimetallic Theranostics: Photophysical Studies

  摘要：

  A series of (eta(6)-p-cymene)ruthenium(II)- and osmium(II) complexes of porphyrin-phosphane derivatives have been synthesized as potential bimetallic theranostic candidates. The photophysical and electrochemical properties were investigated, and these species desirably exhibit no or almost no photoinduced intramolecular atom, energy, and electron transfer between the dye and the metallic fragment. These favorable features are mostly associated with the presence of their long chain (i.e., similar to 1 nm) separating the two functional units. Interestingly, a decrease in emission intensity and lifetimes (up to 35-fold) has been observed, which was ascribed to a small heavy atom effect. This effect is possible as a chain folding driven by an intramolecular H-bond (N-H...ClM).

  DOI：

  10.1021/om5011808

文献信息

• Redox properties of nitrophenylporphyrins and electrosynthesis of nitrophenyl-linked <font>Zn</font> porphyrin dimers or arrays
  作者：Yuanyuan Fang、Xiaoqin Jiang、Zhongping Ou、Clément Michelin、Nicolas Desbois、Claude P. Gros、Karl M. Kadish

  DOI：10.1142/s1088424614500540

  日期：2014.8

  Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH ₂ Cl ₂ containing 0.1 M TBAP. The investigated compounds are represented as ( NO ₂ Ph )_x Ph _4-x PorM , where Por represents the dianion of the porphyrin macrocycle, Ph is a phenyl group on meso-position of the macrocycle, NO ₂ Ph is a meso-substituted nitrophenyl group, M = 2 H , Pd ^II or Zn ^II and x = 1 or 2. Each porphyrin undergoes an initial one electron reduction at E_1/2 = -1.07 to -1.12 V where the added negative charge is almost totally localized on the meso-nitrophenyl group of the compound. This reversible reduction is then followed by one or more irreversible reductions of the nitrophenyl anion at more negative potentials which overlap with reduction of the conjugated porphyrin macrocycle. The initial one electron addition was monitored by thin-layer UV-vis spectroelectrochemistry which confirmed formation of a reduced nitrophenyl group in each case but also gave spectral evidence for a linkage of the one-electron reduction products in the case of the Zn derivatives, giving Zn porphyrin dimers or arrays which are characterized by a 14–15 nm red-shifted Soret band and two well-defined Q-bands, consistent with conversion from an unreduced four coordinate Zn ^II nitrophenylporphyrin to a five-coordinate Zn ^II complex with an unreduced porphyrin macrocycle.

  研究了五种硝基苯卟啉在含有 0.1 M TBAP 的 CH 2 Cl 2 中的电化学特性。所研究的化合物表示为 ( NO 2 Ph )x Ph 4-x PorM，其中 Por 代表卟啉大环的二元离子，Ph 是大环中间位置上的苯基，NO 2 Ph 是中间取代的硝基苯基，M = 2 H、Pd II 或 Zn II，x = 1 或 2。每个卟啉都会在 E1/2 = -1.07 至 -1.12 V 的电压下发生初始的一个电子还原，在这个过程中，增加的负电荷几乎全部集中在化合物的中取代硝基苯基上。在这种可逆还原之后，硝基苯阴离子会在更负的电位下发生一次或多次不可逆还原，这些还原与共轭卟啉大环的还原重叠。薄层紫外-可见光谱电化学法对最初的一个电子加成进行了监测，结果证实在每种情况下都形成了一个还原的硝基苯基团，但在锌衍生物的情况下，还提供了一个电子还原产物连接的光谱证据、这与未还原的四配位 Zn II 硝基苯卟啉转化为带有未还原卟啉大环的五配位 Zn II 复合物相一致。
• A critical evaluation of EFISH and THG non-linear optical responses of asymmetrically substituted meso-tetraphenyl porphyrins and their metal complexes
  作者：Maddalena Pizzotti、Renato Ugo、Elisabetta Annoni、Silvio Quici、Isabelle Ledoux-Rak、Giuseppe Zerbi、Mirella Del Zoppo、PierCarlo Fantucci、Ivana Invernizzi

  DOI：10.1016/s0020-1693(02)01027-7

  日期：2002.11

  The experimental second and third order non-linear optical (NLO) responses gamma(EFISH) and gamma(THG), measured working with a non-resonant incident wavelength of 1.907 mum, of some push-pull meso-tetraphenyl porphyrins and their metal complexes, substituted in the para position of one phenyl ring with a nitro group and with hydrogen or methyl or methoxy groups in the para position of the other three phenyl rings, are critically discussed, also with the support of semiempirical MNDO-TDHF calculations. Care must be taken in evaluating the quadratic hyperpolarizabilities beta(vec) from gamma(EFISH) being the contribution of the cubic term gamma(0)(-2omega; omega, omega, omega) to gamma(EFISH) not negligible at least when the second order NLO response is relatively low, as in porphyrins and their metal complexes investigated in this work. In addition experimental evidence has been produced that the value of gamma(EFISH) of the porphyrins and their metal complexes is increased by resonance enhancement when working with an incident wavelength of 1.34 mum, due to the presence of very strong absorption bands in the region 0.400-0.650 mum and that the gamma(EFISH) response is not significantly affected by 3d(n) (n = 7 - 10) metal coordination. On the contrary gamma(THG) decreases by metal coordination due to the high resonance enhancement of gamma(THG) of free porphyrins. In fact the third harmonic 3omega (0.636 mum) in free porphyrins is quite close to some strong Q absorption bands above 0.615 mum, which are lacking in the absorption spectra of their 3d(n) metal complexes. A vibrational method for the evaluation of the order of magnitude of the static cubic gamma(0) third order NLO response was successfully applied for the first time to a push-pull porphyrinic system. (C) 2002 Elsevier Science B.V. All rights reserved.