nickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin | 689262-20-2

• 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: nickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin
• CAS: 689262-20-2
• 化学式: C₄₆H₂₉N₃Ni
• 分子量: 682.446
• InChiKey: ZIEADVFFECOEOR-XTHWXISQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  盐酸 、 nickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin 以 氯仿 为溶剂， 以99%的产率得到chloronickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin
  参考文献：
  名称：

  Cadmium(II) and Nickel(II) Complexes of Benziporphyrins. A Study of Weak Intramolecular Metal−Arene Interactions

  摘要：

  Weak metal-arene interactions have been investigated in Zn, Cd, Hg, and Ni complexes of meso-tetraaryl m- and p-benziporphyrin (1 and 2) and of the new compound, m-benziporphodimethene (3). Compounds 1-3 incorporate the phenylene moiety into a macrocyclic structure so as to facilitate the interaction between the arene and coordinated metal ion. X-ray studies performed on Cd(II) and Ni(II) complexes show that the arene fragment approaches the ion at a distance much shorter than the sum of van der Waals radii. In chloronickel(II) m-benziporphyrin, a weak agostic bond is actually formed. In the NMR spectra of the Cd(II) and Hg(II) species, unusual H-1-M and C-13-M scalar couplings have been observed that are transmitted directly between the metal and the arene. DFT calculations performed for two Cd(II) species and subsequent AIM analysis show that the accumulation of electron density between the metal and arene necessary to induce these couplings is fairly small and the interaction is steric in nature. In the paramagnetic Ni(II) complexes of 1 and 3, the agostic proton of the m-phenylene exhibits large downfield H-1 NMR shifts (386 and 208 ppm at 298 K, respectively). An agostic mechanism of spin density transfer is proposed to explain these shifts as resulting from electron donation from the CH bond to the metal. In chloronickel(II) p-benziporphyrin, the inner protons of the p-phenylene have a contrastingly small shift (0.0 ppm at 298 K), indicating that in this case the agostic interaction is inefficient, in agreement with the X-ray, data.

  DOI：

  10.1021/ja039384u
• 作为产物：
  描述：

  chloronickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin 在 K₂CO₃ 作用下， 以 乙腈 为溶剂， 生成 nickel(II) 6,11,16,21-tetraphenyl-m-benziporphyrin
  参考文献：
  名称：

  Cadmium(II) and Nickel(II) Complexes of Benziporphyrins. A Study of Weak Intramolecular Metal−Arene Interactions

  摘要：

  Weak metal-arene interactions have been investigated in Zn, Cd, Hg, and Ni complexes of meso-tetraaryl m- and p-benziporphyrin (1 and 2) and of the new compound, m-benziporphodimethene (3). Compounds 1-3 incorporate the phenylene moiety into a macrocyclic structure so as to facilitate the interaction between the arene and coordinated metal ion. X-ray studies performed on Cd(II) and Ni(II) complexes show that the arene fragment approaches the ion at a distance much shorter than the sum of van der Waals radii. In chloronickel(II) m-benziporphyrin, a weak agostic bond is actually formed. In the NMR spectra of the Cd(II) and Hg(II) species, unusual H-1-M and C-13-M scalar couplings have been observed that are transmitted directly between the metal and the arene. DFT calculations performed for two Cd(II) species and subsequent AIM analysis show that the accumulation of electron density between the metal and arene necessary to induce these couplings is fairly small and the interaction is steric in nature. In the paramagnetic Ni(II) complexes of 1 and 3, the agostic proton of the m-phenylene exhibits large downfield H-1 NMR shifts (386 and 208 ppm at 298 K, respectively). An agostic mechanism of spin density transfer is proposed to explain these shifts as resulting from electron donation from the CH bond to the metal. In chloronickel(II) p-benziporphyrin, the inner protons of the p-phenylene have a contrastingly small shift (0.0 ppm at 298 K), indicating that in this case the agostic interaction is inefficient, in agreement with the X-ray, data.

  DOI：

  10.1021/ja039384u

文献信息

• Nonaromatic Organonickel(II) Phototheranostics
  作者：Yuhang Yao、Guangliu Ran、Chun-Liang Hou、Ruijing Zhang、Daniel N. Mangel、Zi-Shu Yang、Mengliang Zhu、Wenkai Zhang、Jing Zhang、Jonathan L. Sessler、Song Gao、Jun-Long Zhang

  DOI：10.1021/jacs.2c00710

  日期：2022.4.27

  theranostics, agents that integrate diagnostic and therapeutic functions within the same molecule, may hold the key to the development of low-cost personalized medicines. Here, we report a set of O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic organonickel(II) complexes, Ni-1–4, containing strong σ-donating M–C bonds. Complexes Ni-1–4 are characterized by a square-planar coordination geometry as inferred

  地球上丰富的基于金属的治疗学，将诊断和治疗功能整合到同一分子中的药物，可能是开发低成本个性化药物的关键。在这里，我们报告了一组 O-连接的非芳族苯并三吡喃 (C^N^N^N) 大环有机镍 (II) 配合物Ni-1 – 4，含有强 σ 供体 M-C 键。配合物Ni-1 – 4的特征在于从Ni-1的结构研究中推断的方形平面配位几何形状。它们将光热疗法、光热成像和光声成像 (PAI) 集成到一个系统中。这使得它们作为潜在的光治疗学具有吸引力。相对于传统的 Ni(II) 卟啉，如F20 TPP（四氟苯基卟啉）， Ni-1的最低能量吸收转移到近红外区域，可能是 Ni-C 键合的结果。超快瞬态吸收光谱与理论计算相结合表明，在光激发下， Ni-1中的配体中心和3 个MLCT 态相对于NiTPBP（TPBP = 6,11,16,21-四苯基苯并卟啉）具有更高的数量。将Ni -1包裹在 1,2-二硬脂酰-sn-甘油-3-磷酸乙醇胺-N-